US20030102222A1 - Deposition method for nanostructure materials - Google Patents
Deposition method for nanostructure materials Download PDFInfo
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- US20030102222A1 US20030102222A1 US09/996,695 US99669501A US2003102222A1 US 20030102222 A1 US20030102222 A1 US 20030102222A1 US 99669501 A US99669501 A US 99669501A US 2003102222 A1 US2003102222 A1 US 2003102222A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to methods of depositing a nanostructure or nanotube-containing material onto a substrate, and associated structures and devices.
- nanostructure material is used by those familiar with the art to designate materials including nanoparticles such as C 60 fullerenes, fullerene-type concentric graphitic particles; nanowires/nanorods such as Si, Ge, SiO x , GeO x , or nanotubes composed of either single or multiple elements such as carbon, B x ,N y , C x B y N z , MoS 2 , and WS 2 .
- One of the common features of nanostructure materials is their basic building blocks.
- a single nanoparticle or a carbon nanotube has a dimension that is less than 500 nm at least in one direction.
- U.S. Pat. No. ______ U.S. patent application Ser. No. 09/817,164 entitled “Coated Electrode With Enhanced Electron Emission And Ignition Characteristics” the disclosure of which is incorporated herein by reference, in its entirety, discloses an electrode including a first electrode material, an adhesion-promoting layer, and a carbon nanotube-containing material disposed on at least a portion of the adhesion promoting layer, as well as associated devices incorporating such an electrode.
- nanostructure materials such as carbon nanotubes possess promising properties, such as electron field emission characteristics which appear to be far superior to that of conventional field emitting materials.
- carbon-nanotube materials exhibit low emission threshold fields as well as large emission current densities. Such properties make them attractive for a variety of microelectronic applications, such as lighting elements, field emission flat panel displays, gas discharge tubes for over voltage protection, and x-ray generating devices.
- carbon nanotubes are produced by techniques such as laser ablation and arc discharge methods. Carbon nanotubes produced by such techniques are collected, subjected to further processes (e.g.—filtration and/or purification) and subsequently deposited or otherwise incorporated into the desired device. Thus, according to these conventional techniques, it is not possible to directly form carbon nanotubes onto a substrate or carrier material.
- Post-formation methods such as screen printing and spraying have been utilized to deposit pre-formed carbon nanotubes on a substrate.
- screen printing requires the use of binder materials as well as an activation step.
- Spraying can be inefficient and is not practical for large-scale fabrication.
- Carbon nanotubes have been grown directly upon substrates by use of chemical vapor deposition (CVD) techniques.
- CVD chemical vapor deposition
- Such techniques require relatively high temperatures (e.g. —600-1,000° C.) as well as reactive environments in order to effectively grow the nanotubes.
- the requirement for such harsh environmental conditions severely limits the types of substrate materials which can be utilized.
- the CVD technique often results in mutli-wall carbon nanotubes. These mutli-wall carbon nanotubes generally do not have the same level of structural perfection and thus have inferior electronic emission properties when compared with single-walled carbon nanotubes.
- the present invention addresses the above-mentioned disadvantages associated with the state of the art, and others.
- the present invention provides a process for depositing pre-formed nanostructure material, such as carbon nanotubes, onto a substrate material utilizing electrophoretic deposition.
- the present invention provides a method of depositing a nanostructure-containing material onto a substrate, the method comprising:
- nanostructure-containing material is caused to migrate toward, and attach to, the substrate.
- the present invention provides a method of attaching a single nanotube or nanowire onto a sharp tip of a sharp object, the method comprising:
- the present invention provides a method of depositing a nanostructure-containing multi-layer structure onto substrate, the method comprising:
- nanostructure-containing material is caused to migrate toward, and attach to, the exposed areas on the substrate.
- the present invention provides a method of depositing a pattern of nanostructure-containing material onto a substrate, the method comprising:
- nanostructure-containing material is caused to migrate toward, and attach to, those exposed areas on the first surface of the substrate;
- FIG. 1A is a transmission electron microscopic (TEM) image of purified single walled carbon nanotube bundles.
- FIG. 1B is a TEM image of single walled carbon nanotubes etched to a 4 micron average bundle length.
- FIG. 1C is a TEM image of single walled carbon nanotubes etched to a 0.5 micron average bundle length.
- FIG. 2 is a schematic illustration of an electrophoretic deposition process according to the principles of the present invention.
- FIG. 3A is a scanning electron microscope (SEM) image of a coating of “long ” single-walled carbon nanotubes onto a substrate according to the principles of the present invention.
- FIG. 3B is a SEM image of a coating of “short” single-walled carbon nanotubes onto a substrate according to the principles of the present invention.
- FIG. 4 is a plot of the measured electron field emission current versus the applied electrical field from a single-wall carbon nanotube films formed by the process of the present invention.
- FIG. 5A is a schematic illustration of a process according to the present invention used to attach a bundle or a single carbon nanotube or a nanowire to an object with a sharp tip.
- FIG. 5B is a schematic illustration of the sharp tip having an attached single carbon nanotube or nanowire formed according to a process as depicted in FIG. 5A.
- FIG. 5C is an SEM image the sharp tip having an attached single carbon nanotube or nanowire formed according to a process of the present invention.
- FIG. 6A- 6 C are a schematic illustrations of a selective deposition process performed according to the present invention.
- FIGS. 7A and 7B are SEM images showing a top view of a coated surface of a multi-layer structure formed according to a selective deposition process as illustrated in FIGS. 6 A- 6 C.
- FIGS. 8 A- 8 C are schematic illustrations of an embodiment of a selective deposition process according to the present invention.
- FIG. 8D is a side view of an embodiment of a patterned substrate formed according to the process of FIGS. 8 A- 8 C.
- a method performed according to the principles of the present invention can include a combination of some or all of the following steps: (1) forming a solution or suspension containing the nanostructure material; (2) selectively adding “chargers” to the solution; (3) immersing electrodes in the solution, the substrate upon which the nanostructure material is to be deposited acting as one of the electrodes; (4) applying a direct and/or alternating current thus creating an electrical field between the electrodes for a certain period of time thereby causing the nanostructure materials in the solution to migrate toward and attach themselves to the substrate electrode; and (5) optional subsequent processing of the coated substrate.
- the process begins with pre-formed raw nanostructure or nanotube-containing material, such as a carbon nanotube-containing material.
- This raw nanotube material can comprise at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes.
- the raw carbon nanotube-containing material comprises single-walled carbon nanotubes.
- the raw carbon-containing material can be fabricated according to a number of different techniques familiar to those in the art.
- the raw carbon nanotube-containing material can be fabricated by laser ablation techniques (e.g.—see U.S. Pat. No. 6,280,697), chemical vapor deposition techniques (see, e.g.—C. Bower et al., “Plasma Induced Conformal Alignment of Carbon Nanotubes on Curvatured Surfaces,” Appl Phys Lett. Vol. 77, No. 6, pgs. 830-32 (2000)), or arc-discharge techniques (see, e.g.—C. Journet et al., Nature, Vol. 388, p. 756 (1997)).
- laser ablation techniques e.g.—see U.S. Pat. No. 6,280,697
- chemical vapor deposition techniques see, e.g.—C. Bower et al., “Plasma Induced Conformal Alignment
- These raw materials can be formed by any suitable technique, such as the above-mentioned arc-discharge technique.
- the raw materials are in the form of nanowires with at least one of the following: elemental metal, Si, Ge, oxide, carbide, nitride, chalcogenide.
- the raw materials can be in the form of nanoparticles of elemental metal, metal oxide, elemental and compound semiconducting materials.
- the raw carbon nanotube-containing material is subjected to purification.
- a suitable solvent such as a combination of peroxide (H 2 O 2 ) and water, with an H 2 O 2 concentration of 1-40% by volume, preferably about 20% by volume H 2 O 2 , with subsequent rinsing in CS 2 and then in methanol, followed by filtration.
- H 2 O 2 peroxide
- CS 2 peroxide
- methanol methanol
- the raw carbon nanotube-containing material is placed in a suitable liquid medium, such as an acidic medium, an organic solvent, or an alcohol, preferably methanol.
- a suitable liquid medium such as an acidic medium, an organic solvent, or an alcohol, preferably methanol.
- the nanotubes are kept in suspension within the liquid medium for several hours using a high-powered ultrasonic horn, while the suspension is passed through a microporous membrane.
- the raw materials can be purified by oxidation in air or an oxygen environment at a temperature of 200-700° C. The impurities in the raw materials are oxidized at a faster rate than the nanotubes.
- the raw materials can be purified by liquid chromatography to separate the nanotubes/nanowires from the impurities.
- the raw material is then optionally subjected to further processing to shorten the nanotubes and nanotube bundles, such as chemical etching.
- the purified carbon nanotube material can be subjected to oxidation in a strong acid.
- purified carbon nanotube material can be placed in an appropriate container in a solution of acid comprising H 2 SO 4 and HNO 3 .
- the carbon nanotubes in solution are then subjected to sonication for an appropriate length of time.
- the processed nanotubes are collected from the acid solution by either filtration or centrifuging after repeated dilution with de-ionized water.
- FIG. 1A An illustrative example of such a process is described as follows.
- Purified raw material formed as described above was found to contain approximately 90% single-walled nanotube bundles over 10 ⁇ m in length and 5-50 mn in bundle diameter. Such “long” nanotube bundles are illustrated by FIG. 1A.
- This material was chemically etched in a solution of H 2 SO 4 and HNO 3 for 10-24 hours while being subjected to ultrasonic energy. After etching the single wall carbon nanotube bundles etched for 20 hours had an average length of 4 ⁇ m and the single wall carbon nanotube bundles etched for 24 hours had an average bundle length of 0.5 ⁇ m, as shown by the transmission electron microscopy images in FIGS. 1B - 1 C.
- the purified materials can be chemically functionalized by, for example, chemically or physically attaching chemical species to the outer surfaces of the carbon nanotubes such that they will be either soluble or form stable suspensions in certain solvents.
- the purified raw material can be shortened by mechanical milling.
- a sample of the purified carbon nanotube material is placed inside a suitable container, along with appropriate milling media.
- the container is then shut and placed within a suitable holder of a ball-milling machine.
- the time that the sample is milled can vary. An appropriate amount of milling time can be readily determined by inspection of the milled nanotubes.
- the preferred length of the shortened material is approximately 0.1-100 micrometers, preferably 0.1-10 micrometers, and more preferably 0.3-3.0 micormeters.
- the purified raw material can also optionally be annealed at a suitable temperature, such as 100° C.-1200° C. According to a preferred embodiment, the annealing temperature is 100° C.-600° C.
- the material is annealed for a suitable time period, such as approximately 1 to 60 minutes. According to a preferred embodiment, the material is annealed for approximately 1 hour.
- the material is annealed in a vacuum of about 10 ⁇ 2 torr, or at an even higher vacuum pressure. According to a preferred embodiment, the vacuum is about 5 ⁇ 10 ⁇ 7 torr.
- a suitable liquid medium is selected which will permit the formation of a stable suspension of the raw nanostructure material therein.
- the liquid medium comprises at least one of water, methanol, ethanol, alcohol, and dimethylformamide (DMF).
- the liquid medium comprises ethanol.
- the mixture can optionally be subjected to ultrasonic energy or stirring using, for example, a magnetic stirrer bar, in order to facilitate the formation of a stable suspension.
- the amount of time that the ultrasonic energy is applied can vary, but it has been found that approximately two hours at room temperature is sufficient.
- the concentration of raw material in the liquid medium can be varied, so long as a stable suspension is formed.
- a liquid medium comprising methanol approximately 0.01 mg of the raw material, such as single-walled carbon nanotubes, can be present per ml of the liquid medium (0.01 mg/ml) and provide a stable suspension.
- the liquid medium comprises DMF
- approximately 0.4-0.5 mg of the raw material, such as single-walled carbon nanotubes can be present per ml of the liquid medium (0.4-0.5 mg/ml) and provide a stable suspension.
- shortened carbon nanotubes are used, stable suspension can be obtained at a higher concentration. For example, a stable dispersion of approximately 0.1 mg/ml of shortened nanotubes in water can be formed.
- a “charger” is added to the suspension in order to facilitate electrophoretic deposition.
- One such preferred charger is MgCl 2 .
- Some other chargers include Mg(NO 3 ) 2 , La(NO 3 ) 3 , Y(NO 3 ) 3 , AlCl 3 , and sodium hydroxide. Any suitable amount can be utilized. Amounts ranging from less than 1% up to 50%, by weight, as measured relative top to the amount of nanostructure-containing material, are feasible. According to a preferred embodiment, the suspension can contain less than 1% of the charger.
- a plurality of electrodes are then introduced into the suspension.
- two electrodes are utilized.
- One of the electrodes comprises the substrate upon which the nanostructure material is to be deposited. Any suitable substrate material is envisioned, so long as it possesses ⁇ the requisite degree of electrical conductivity.
- the substrate is either metal or doped silicon.
- Electrodes An alternating current, or a direct current is applied to the electrodes thereby producing an electrical field between the electrodes. This causes the nanotstructure material in the suspension to migrate toward and attach to the substrate electrode.
- the electrical field applied between electrodes is 0.1-1000 V/cm, and a direct current of 0.1-200 mA/cm 2 is applied for 1 second-1 hour.
- FIG. 2 is a schematic illustration of the above-described process.
- a pair of electrodes E 1 and E 2 are introduced into the suspension S susp .
- the electrodes E 1 and E 2 are connected to a power supply P, which produces an electrical field between E 1 and E 2 .
- the nanostructure material will migrate toward and attach to one of the electrodes thereby forming a coating C of the nanostructure material on one of the electrodes.
- the substrate S sub is the negative electrode E 1 , or anode.
- the above-described electrophoretic deposition is carried out at room temperature.
- the rate of deposition of the coating C, as well as its structure and morphology can be influenced by many factors. Such factors include: the concentration of nanostructure material in the suspension S susp , the concentration of the charger material (e.g. —MgCl 2 ) in the suspension S susp , the conductivity of the substrate, and control of the power source P.
- concentration of nanostructure material in the suspension S susp the concentration of the charger material (e.g. —MgCl 2 ) in the suspension S susp
- the conductivity of the substrate e.g. —MgCl 2
- a stainless steel substrate/electrode and a counter electrode were introduced into a suspension comprising DMF and single-walled carbon nanotubes at a concentration of 0.4 mg/ml, and MgCl 2 .
- a direct current was applied resulting in an electrical field of approximately 20 V/cm formed between the electrodes.
- Application of the current for about 30 seconds results in the formation of a smooth film of single-walled carbon nanotubes on the substrate.
- a thin film of single-walled carbon nanotubes approximately 1 micrometer thick was deposited on the substrate. This film was examined using a scanning electron microscope, and is illustrated in FIG. 3A.
- the morphology of the deposited coating or film is similar to that of coating or film applied by spraying, and comprises clearly defined single-walled carbon nanotube bundles.
- FIG. 3B is a SEM image of a coating of single-walled carbon nanotube bundles deposited by electrophoretic deposition in the manner described above. However, the nanotubes were subjected to a previously described process to shorten their length (e.g.—to about a 0.5 ⁇ m average bundle length).
- the film depicted in FIG. 3 was densified by sintering in vacuum at a suitable temperature (e.g.—800° C.). This coating comprises distinct grain boundaries with densely packed grains. Individual single-walled carbon nanotube bundles are no longer discernable.
- the particular electrode (i.e.—anode or the cathode) to which the nanostructure material migrates can be controlled through the selection of the charger material.
- a “negative” charger such as sodium hydroxide (NaOH) imparts a negative charge to the nanostructure material, thereby creating a tendency for the nanostructure material to migrate towards the positive electrode (cathode).
- a “positive” charger material such as MgCl 2 , a positive charge is imparted to the nanostructure material, thereby creating a tendency for the nanostructure material to migrate toward the negative electrode (anode).
- the electrodes are removed from the suspension after a suitable deposition period.
- the coated substrate electrode may optionally be subjected to further processing.
- the coated substrate may be annealed to remove the liquid medium.
- Such an annealing procedure may be preferable, since removal of impurities such as residual suspension medium improves the emission characteristics of the nanostructure material.
- the coated substrate can be heated to a temperature of approximately 100-1200° C. for approximately 1 hour, and then at approximately 800° C. for 2 hours, both at a vacuum of approximately 5 ⁇ 10 ⁇ 7 torr.
- SWNT single-walled carbon nanotubes
- the threshold field is defined as the electrical field required for the emission current density to reach 0.01 mA/cm 2 .
- the current decay is calculated by (I initial -I final )/I initial , where I initial is the initial emission current and I final is the emission current after 10 h of measurement.
- Initial emission Emission current Threshold field current density decay after 10 hours Materials [V/micrometer] [mA/cm 2] [%] As-grown SWNT 1.3 200 50 mat Purified SWNT 1.0 93 40 paper (made by filtration) CVD SWNT film 3.1 10 79 [a] EPD long SWNT 1.4 83 3 film
- FIG. 4 is a plot of the total electron field emission current versus applied voltage for two samples of nanotube films A and B.
- Sample A was formed as previously described, using methanol as a suspension media.
- Sample B was formed using DMF as a suspension media.
- the measurements were made over a 6 mm 2 emissions area at a cathode-anode distance of 160 ⁇ m at a base pressure of 2 ⁇ 10 ⁇ 7 torr.
- the inset portion of FIG. 4 represents the same data plotted as I/V 2 versus I/V, which shows a substantially linear behavior which is indicative of field emission of electrons.
- a film is formed having a threshold field for emission of less than 1.5 volts/micrometer.
- the film can produce an emission current density greater than 1 A/cm 2 .
- the film can produce a total emission current greater than 10 mA over a 6 mm 2 area.
- the film can also produce a pulsed emission current having a pulse frequency higher than 10 KHz, preferably higher than 100 KHz.
- the total pulsed current measured over a 6 mm 2 area is preferably higher than 10 mA at 10-12 V/ ⁇ m.
- the emission current is capable of being consistently reproduced, without decay, even after a number of pulsed emissions, as evidenced by the above data.
- the pulsed current is stable and higher than 10 mA over a 6 mm 2 area for at least 1,000 pulses, preferably for at least 10,000 pulses.
- the single-walled carbon nanotube film formed according to the principles of the present invention exhibit excellent field emission characteristics, especially in the area of resistance to emission current density decay.
- the coating of nanostructure materials deposited according to the principles of the present invention exhibit better adhesion that a similar coatings applied by other techniques such as spraying. While not wishing to be limited by any particular theory, the improved adhesion may be due to the formation of metal hydroxide on the surface of the substrate (formed from metal ions of the electrode and OH groups from the charger).
- the films formed according to the principles of the present invention also exhibit improved field emission stability (i.e.—higher resistance to field emission decay).
- the adhesion of nanotubes to the substrate can be further improved by incorporation of adhesion promoting materials such as binders, carbon-dissolving or carbide-forming metal and high temperature annealing.
- adhesion promoting materials such as binders, carbon-dissolving or carbide-forming metal and high temperature annealing.
- These materials can be introduced by, for example, one of the following processes: co-deposition of the nanostructures and particles of adhesion promoting materials, sequential deposition, pre-deposition of a layer of adhesion promoting materials, etc.
- binders such as polymer binders are added to the suspension of the nanostructure-containing material which is then either stirred or sonicated to obtain a uniform suspension.
- Suitable polymer binders include poly(vinyl butyral-co vinyl alcohol-co-vinyl acetate) and poly(vinylidene fluoride).
- Suitable chargers are chosen such that under the applied electrical field, either DC or AC, the binder and the nanostructures would migrate to the same electrodes to form a coating with an intimate mixing of the nanostructures and the binder.
- small metal particles such as titanium, iron, lead, tin, cobalt are mixed into the suspension of the nanostructure-containing material.
- Suitable chargers are chosen such that under the applied electrical field, the metal particles and the nanostructures will migrate to the desired electrode to form a uniform coating with an intimate mixing of the metal particles and the nanostructures.
- the coated substrate is annealed in vacuum with a base vacuum pressure of 10 ⁇ 3 torr or greater for 0.1-10 hours.
- the diameter of the particles is smaller than 1 micrometer.
- the binders or adhesion promoting materials can be added in any suitable amount. Amounts ranging from 0.1-20% by weight, measured relative to the amount of nanostructure-containing material is envisioned.
- the substrate to be coated with the nanostructures is first coated with at least one layer of adhesion-promoting metal such as titanium, iron, lead, tin, cobalt, nickel, tantalum, tungsten, niobium, zirconium, vanadium, chromium or hafnium.
- adhesion-promoting metal such as titanium, iron, lead, tin, cobalt, nickel, tantalum, tungsten, niobium, zirconium, vanadium, chromium or hafnium.
- the layer can be applied by techniques such as electrochemical plating, thermal evaporation, sputtering or pulsed laser deposition.
- the film is annealed in vacuum with a base vacuum pressure of 10 ⁇ 3 torr or greater for 0.1-10 hours.
- the above-described processes are advantageously well-adapted for high output and automation. These processes are very versatile and can be used to form uniform coatings of various thicknesses (e.g.—tens of nanometers to a few micrometers thick), coatings on complex shapes, as well as complicated structures such as composites and “gated” electrodes.
- the methods of the present invention are useful in producing nanotube materials which have properties that make them beneficial for use in a number of different applications.
- the method of the present invention is especially beneficial in providing nanotube material for incorporation into electron field emission cathodes for devices such as x-ray generating devices, gas discharge tubes, lighting devices, microwave power amplifiers, ion guns, electron beam lithography devices, high energy accelerators, free electron lasers, electron microscopes and microprobes, and flat panel displays.
- devices such as x-ray generating devices, gas discharge tubes, lighting devices, microwave power amplifiers, ion guns, electron beam lithography devices, high energy accelerators, free electron lasers, electron microscopes and microprobes, and flat panel displays.
- the electrophoresis method of the present invention can be used to coat substrates with composite layers in which nanostructured materials serve as one of the components. It can also be utilized to form multilayered structures on a supporting surface.
- nanostructured materials and at least one more component are suspended in a liquid medium to make up the electrophoresis bath.
- a “charger” to the suspension, two electrodes, wherein at least one of the electrodes comprises the substrate, are immersed in the suspension and a direct or alternating current is applied to the immersed electrodes thereby creating an electrical field between the electrodes. Because the nanostructured materials and the other component in the suspension are charged by the same “charger”, they would migrate toward and attach to the same substrate simultaneously under the same electrical field.
- the composition of deposited composite layer is mostly decided by the composition of the suspension in which the electrophoresis has been carried out. Therefore, composite layers having different composition can be readily obtained by immersing a substrate in baths with deferent compositions and performing the above-described electrophoretic deposition.
- a composite layer can be made by electrophoresis using only one bath, multiple baths can be used to produce a multilayered electrophoretic deposition.
- the electrophoresis is carried out in each bath sequentially with each bath producing a layer of different composition in the multilayered structure.
- the deposition electrode can be moved to the next suspension for deposition of the next layer.
- the electrophoretic deposition technique disclosed can be further applied to deposit an individual or a bundle of carbon nanotubes or nanowires selectively onto a sharp tip.
- This sharp tip can be, for example, the tip used for microscopes including atomic force microscopes, scanning tunneling microscopes, or profilometers.
- FIGS. 5 A- 5 B One such embodiment is illustrated in FIGS. 5 A- 5 B, where a dilute suspension of nanotube or nanowire is first prepared.
- a counter electrode 510 is first immersed into the suspension 520 .
- the metal tip 530 is used as the second electrode. It is first placed perpendicular to the suspension surface with the sharp tip, where the nanotube/nanowire is to be deposited, just slightly above the top surface of the suspension. The tip is then gradually moved towards the surface of the suspension.
- a meter such as a current meter 540 is used to monitor the electrical current between the counter electrode and the metal tip.
- an appropriate optical magnification device can be used to monitor the gap between the metal tip 530 and the suspension surface 520 .
- FIG. 5C is an SEM image of a sharp tip having a single nanotube or nanowire deposited thereon according to the techniques of the present invention.
- triode-type structures with nanostructured field emission materials deposited in selected areas.
- Such structures can be used, for example, in field emission flat panel displays; cold cathodes for x-ray tubes, microwave amplifiers, etc.
- FIGS. 6 A- 7 B In one embodiment of this application is illustrated in FIGS. 6 A- 7 B, where a multilayer structure comprising a Si substrate 610 , a dielectric insulating layer 620 such as silicon dioxide, a conducting layer 630 and a layer of photoresist 640 is fabricated by common thin film fabrication techniques (FIG. 6A). A photo-mask is used to selectively expose the photoresist 640 to ultraviolet light. The multilayer structure is then developed using suitable chemicals to remove the exposed underlying multi-layer structure at the desired locations (FIG. 6B). As illustrated in FIG. 6B, the dimension D of the exposed areas of substrate 610 is small. For example, D can be on the order of 1-100 micrometers, preferably 5-20 micrometers.
- the exposed areas can be in the form of an array of rounded holes or polygons such as squares.
- carbon nanotubes or other nanostructures are selectively deposited on the exposed Si surfaces of substrate 610 by electrophoresis.
- the chemical etched structure is immersed into a carbon nanotube suspension.
- Contact to the power source is made on the back of surface 610 .
- a metal plate is used as the counter electrode.
- a bias voltage is also preferably applied to the conductive surface 630 to prevent deposition of carbon nanotubes on the metal surface. Under the applied electrical field, carbon nanotubes will migrate to the exposed surfaces of substrate 610 .
- the dielectric layer 620 can have a thickness on the order of 1-100 micrometers, preferably 1-10 micrometers.
- FIG. 7A and 7B show the top view of the etched multi-layer structures formed as described above.
- the electrophoresis method of the present invention can also be utilized to form a patterned deposit of nanostructure-containing material onto a substrate.
- FIGS. 8A to 8 D illustrate one embodiment of this application.
- a mask 640 is placed on top of a first surface of a substrate 650 before electrophoresis.
- the area 670 on the surface of substrate 650 where no deposition is intended is blocked by the mask 640 , while the areas 660 on the surface of substrate 650 are exposed to the electrophoresis bath through corresponding openings in the mask 640 .
- the masked substrate is then introduced into a suspension and coated by electrophoresis in a manner consistent with the present invention, as set forth in detail above.
- the mask 640 is removed from the substrate 650 and a clean patterned structures 680 containing nanostructure-containing material is obtained, as illustrated in FIG. 8D.
- the dimension(s) and shape(s) of the patterned structures are defined by the openings of the mask 640 .
- FIGS. 8A and 8B show the side and the top view of the mask-blocked substrate before electrophoresis.
- FIG. 8C shows the side view of the mask-blocked substrate after electrophoresis.
- FIG. 8D is the side view of the final structures on the substrate.
Abstract
Description
- [0001] At least some aspects of this invention were made with Government support under contract no. N00014-98-1-05907. The Government may have certain rights in this invention.
- The present invention relates to methods of depositing a nanostructure or nanotube-containing material onto a substrate, and associated structures and devices.
- In the description of the background of the present invention that follows reference is made to certain structures and methods, however, such references should not necessarily be construed as an admission that these structures and methods qualify as prior art under the applicable statutory provisions. Applicants reserve the right to demonstrate that any of the referenced subject matter does not constitute prior art with regard to the present invention.
- The term “nanostructure” material is used by those familiar with the art to designate materials including nanoparticles such as C60 fullerenes, fullerene-type concentric graphitic particles; nanowires/nanorods such as Si, Ge, SiOx, GeOx, or nanotubes composed of either single or multiple elements such as carbon, Bx,Ny, CxByNz, MoS2, and WS2. One of the common features of nanostructure materials is their basic building blocks. A single nanoparticle or a carbon nanotube has a dimension that is less than 500 nm at least in one direction. These types of materials have been shown to exhibit certain properties that have raised interest in a variety of applications and processes.
- U.S. Pat. No. 6,280,697 to Zhou et al. (entitled “Nanotube-Based High Energy Material and Method”), the disclosure of which is incorporated herein by reference, in its entirety, discloses the fabrication of carbon-based nanotube materials and their use as a battery electrode material.
- U.S. Pat. No. ______ (U.S. patent application Ser. No. 09/296,572 entitled “Device Comprising Carbon Nanotube Field Emitter Structure and Process for Forming Device”) the disclosure of which is incorporated herein by reference, in its entirety, discloses a carbon nanotube-based electron emitter structure.
- U.S. Patent No. ______ (U.S. patent application Ser. No. 09/351,537 entitled “Device Comprising Thin Film Carbon Nanotube Electron Field Emitter Structure”), the disclosure of which is incorporated herein by reference, in its entirety, discloses a carbon-nanotube field emitter structure having a high emitted current density.
- U.S. Pat. No. 6,277,318 to Bower et al. (entitled “Method for Fabrication of Patterned Carbon Nanotube Films”), the disclosure of which is incorporated herein by reference, in its entirety, discloses a method of fabricating adherent, patterned carbon nanotube films onto a substrate.
- U.S. Pat. No. ______ (U.S. patent application Ser. No. 09/594,844 entitled “Nanostructure-Based High Energy Material and Method”), the disclosure of which is incorporated herein by reference, in its entirety, discloses a nanostructure alloy with alkali metal as one of the components. Such materials are described as being useful in certain battery applications.
- U.S. Pat. No. ______ (U.S. patent application Ser. No. 09/679,303 entitled “X-Ray Generating Mechanism Using Electron Field Emission Cathode”), the disclosure of which is incorporated herein by reference, in its entirety, discloses an X-ray generating device incorporating a nanostructure-containing material.
- U.S. Pat. No. ______ (U.S. patent application Ser. No. 09/817,164 entitled “Coated Electrode With Enhanced Electron Emission And Ignition Characteristics”) the disclosure of which is incorporated herein by reference, in its entirety, discloses an electrode including a first electrode material, an adhesion-promoting layer, and a carbon nanotube-containing material disposed on at least a portion of the adhesion promoting layer, as well as associated devices incorporating such an electrode.
- U.S. Pat. No. ______ (U.S. patent application Ser. No. 09/881,684 entitled “Method of Making Nanotube-Based Material With Enhanced Field Emission”) the disclosure of which is incorporated herein by reference, in its entirety, discloses a technique for introducing a foreign species into the nanotube-based material in order to improve the emission properties thereof.
- As evidenced by the above, nanostructure materials, such as carbon nanotubes possess promising properties, such as electron field emission characteristics which appear to be far superior to that of conventional field emitting materials. In particular, carbon-nanotube materials exhibit low emission threshold fields as well as large emission current densities. Such properties make them attractive for a variety of microelectronic applications, such as lighting elements, field emission flat panel displays, gas discharge tubes for over voltage protection, and x-ray generating devices.
- However, the effective incorporation of such materials into these devices has been hindered by difficulties encountered in the processing of such materials. For instance, carbon nanotubes are produced by techniques such as laser ablation and arc discharge methods. Carbon nanotubes produced by such techniques are collected, subjected to further processes (e.g.—filtration and/or purification) and subsequently deposited or otherwise incorporated into the desired device. Thus, according to these conventional techniques, it is not possible to directly form carbon nanotubes onto a substrate or carrier material.
- Post-formation methods such as screen printing and spraying have been utilized to deposit pre-formed carbon nanotubes on a substrate. However, such techniques pose certain drawbacks. For instance, screen printing requires the use of binder materials as well as an activation step. Spraying can be inefficient and is not practical for large-scale fabrication.
- Carbon nanotubes have been grown directly upon substrates by use of chemical vapor deposition (CVD) techniques. However, such techniques require relatively high temperatures (e.g. —600-1,000° C.) as well as reactive environments in order to effectively grow the nanotubes. The requirement for such harsh environmental conditions severely limits the types of substrate materials which can be utilized. In addition, the CVD technique often results in mutli-wall carbon nanotubes. These mutli-wall carbon nanotubes generally do not have the same level of structural perfection and thus have inferior electronic emission properties when compared with single-walled carbon nanotubes.
- Thus, there is a need in the art to address the above-mentioned disadvantages, and others, associated with conventional fabrication techniques.
- The present invention addresses the above-mentioned disadvantages associated with the state of the art, and others.
- For example, the present invention provides a process for depositing pre-formed nanostructure material, such as carbon nanotubes, onto a substrate material utilizing electrophoretic deposition.
- According to one embodiment, the present invention provides a method of depositing a nanostructure-containing material onto a substrate, the method comprising:
- (i) forming a suspension of pre-formed nanostructure-containing material in a liquid medium;
- (ii) selectively adding one or more chemicals (“chargers”) to the liquid medium;
- (iii) immersing two electrodes in the suspension, wherein at least one of the electrodes comprises the substrate; and
- (iv) applying a direct or alternating current to the immersed electrodes thereby creating an electrical field between the electrodes;
- whereby the nanostructure-containing material is caused to migrate toward, and attach to, the substrate.
- According to another embodiment, the present invention provides a method of attaching a single nanotube or nanowire onto a sharp tip of a sharp object, the method comprising:
- (i) forming a suspension of pre-formed nanostructure-containing material in a liquid medium;
- (ii) selectively adding a charger to the liquid medium;
- (iii) immersing at least one electrode in the suspension;
- (iv) placing the sharp tip directly above the surface of the suspension and on a stage where the tip can be moved closer or further away from the surface of the suspension; and
- (v) applying a direct or alternating current to the immersed electrode and the sharp object and electrically connecting a current meter to the sharp tip.
- According to yet another embodiment, the present invention provides a method of depositing a nanostructure-containing multi-layer structure onto substrate, the method comprising:
- (i) providing a multilayer structure comprising a substrate and a plurality of additional layers disposed on the substrate;
- (ii) providing a plurality of exposed areas on a surface of the substrate;
- (iii) forming a suspension of pre-formed nanostructure-containing material in a liquid medium;
- (iv) selectively adding a charger to the liquid medium;
- (v) immersing at least one electrode and the multilayer structure in the suspension;
- (vi) applying a direct or alternating current to the electrode and the multilayer structure thereby creating an electrical field therebetween;
- whereby the nanostructure-containing material is caused to migrate toward, and attach to, the exposed areas on the substrate.
- According to another embodiment, the present invention provides a method of depositing a pattern of nanostructure-containing material onto a substrate, the method comprising:
- (i) providing a substrate having a first surface with a mask disposed thereon, the mask having openings through which areas of the first surface are exposed;
- (ii) forming a suspension of pre-formed nanostructure-containing material in a liquid medium;
- (iii) selectively adding a charger to the liquid medium;
- (iv) immersing at least one electrode and the masked substrate in the suspension;
- (v) applying a direct or alternating current to the electrode and the masked substrate thereby creating an electrical field therebetween;
- whereby the nanostructure-containing material is caused to migrate toward, and attach to, those exposed areas on the first surface of the substrate; and
- (vi) removing the mask.
- FIG. 1A is a transmission electron microscopic (TEM) image of purified single walled carbon nanotube bundles.
- FIG. 1B is a TEM image of single walled carbon nanotubes etched to a 4 micron average bundle length.
- FIG. 1C is a TEM image of single walled carbon nanotubes etched to a 0.5 micron average bundle length.
- FIG. 2 is a schematic illustration of an electrophoretic deposition process according to the principles of the present invention.
- FIG. 3A is a scanning electron microscope (SEM) image of a coating of “long ” single-walled carbon nanotubes onto a substrate according to the principles of the present invention.
- FIG. 3B is a SEM image of a coating of “short” single-walled carbon nanotubes onto a substrate according to the principles of the present invention.
- FIG. 4 is a plot of the measured electron field emission current versus the applied electrical field from a single-wall carbon nanotube films formed by the process of the present invention.
- FIG. 5A is a schematic illustration of a process according to the present invention used to attach a bundle or a single carbon nanotube or a nanowire to an object with a sharp tip.
- FIG. 5B is a schematic illustration of the sharp tip having an attached single carbon nanotube or nanowire formed according to a process as depicted in FIG. 5A.
- FIG. 5C is an SEM image the sharp tip having an attached single carbon nanotube or nanowire formed according to a process of the present invention.
- FIG. 6A-6C are a schematic illustrations of a selective deposition process performed according to the present invention.
- FIGS. 7A and 7B are SEM images showing a top view of a coated surface of a multi-layer structure formed according to a selective deposition process as illustrated in FIGS.6A-6C.
- FIGS.8A-8C are schematic illustrations of an embodiment of a selective deposition process according to the present invention.
- FIG. 8D is a side view of an embodiment of a patterned substrate formed according to the process of FIGS.8A-8C.
- A method performed consistent with the principles of the present invention, and according to a preferred embodiment, along with corresponding structures and devices, are described as follows.
- Generally, a method performed according to the principles of the present invention can include a combination of some or all of the following steps: (1) forming a solution or suspension containing the nanostructure material; (2) selectively adding “chargers” to the solution; (3) immersing electrodes in the solution, the substrate upon which the nanostructure material is to be deposited acting as one of the electrodes; (4) applying a direct and/or alternating current thus creating an electrical field between the electrodes for a certain period of time thereby causing the nanostructure materials in the solution to migrate toward and attach themselves to the substrate electrode; and (5) optional subsequent processing of the coated substrate.
- The process begins with pre-formed raw nanostructure or nanotube-containing material, such as a carbon nanotube-containing material. This raw nanotube material can comprise at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes. According to a preferred embodiment, the raw carbon nanotube-containing material comprises single-walled carbon nanotubes.
- The raw carbon-containing material can be fabricated according to a number of different techniques familiar to those in the art. For example, the raw carbon nanotube-containing material can be fabricated by laser ablation techniques (e.g.—see U.S. Pat. No. 6,280,697), chemical vapor deposition techniques (see, e.g.—C. Bower et al., “Plasma Induced Conformal Alignment of Carbon Nanotubes on Curvatured Surfaces,” Appl Phys Lett. Vol. 77, No. 6, pgs. 830-32 (2000)), or arc-discharge techniques (see, e.g.—C. Journet et al., Nature, Vol. 388, p. 756 (1997)).
- It is also contemplated by the present invention that raw materials be in the form of nanotube structures with a composition of Bx,Cy, Nz, (B=boron, C =carbon, and N=nitrogen), or nanotube or concentric fullerene structures with a composition MS2 (M=tungsten, molybdenum, or vanadium oxide) can be utilized. These raw materials can be formed by any suitable technique, such as the above-mentioned arc-discharge technique.
- It is also within the scope of the present invention that the raw materials are in the form of nanowires with at least one of the following: elemental metal, Si, Ge, oxide, carbide, nitride, chalcogenide. In addition, the raw materials can be in the form of nanoparticles of elemental metal, metal oxide, elemental and compound semiconducting materials.
- Next, the raw carbon nanotube-containing material is subjected to purification. A number of techniques for purifying the raw materials are envisioned. According to one preferred embodiment, the raw material can be purified by reflux in a suitable solvent, such as a combination of peroxide (H2O2) and water, with an H2O2 concentration of 1-40% by volume, preferably about 20% by volume H2O2, with subsequent rinsing in CS2 and then in methanol, followed by filtration. According to an exemplary technique, approximately 10-100 ml of peroxide is introduced into the medium for every 1-10 mg of nanotubes in the medium, and the reflux reaction is carried out at a temperature of 20-100° C. (see, e.g.—U.S. Pat. No. ______ (U.S. patent application Ser. No. 09/679,303)).
- According to another alternative, the raw carbon nanotube-containing material is placed in a suitable liquid medium, such as an acidic medium, an organic solvent, or an alcohol, preferably methanol. The nanotubes are kept in suspension within the liquid medium for several hours using a high-powered ultrasonic horn, while the suspension is passed through a microporous membrane. In another embodiment, the raw materials can be purified by oxidation in air or an oxygen environment at a temperature of 200-700° C. The impurities in the raw materials are oxidized at a faster rate than the nanotubes.
- In yet another embodiment, the raw materials can be purified by liquid chromatography to separate the nanotubes/nanowires from the impurities.
- The raw material is then optionally subjected to further processing to shorten the nanotubes and nanotube bundles, such as chemical etching.
- According to one embodiment, the purified carbon nanotube material can be subjected to oxidation in a strong acid. For instance, purified carbon nanotube material can be placed in an appropriate container in a solution of acid comprising H2SO4 and HNO3. The carbon nanotubes in solution are then subjected to sonication for an appropriate length of time. After sonication, the processed nanotubes are collected from the acid solution by either filtration or centrifuging after repeated dilution with de-ionized water.
- An illustrative example of such a process is described as follows. Purified raw material formed as described above was found to contain approximately 90% single-walled nanotube bundles over 10 μm in length and 5-50 mn in bundle diameter. Such “long” nanotube bundles are illustrated by FIG. 1A. This material was chemically etched in a solution of H2SO4 and HNO3 for 10-24 hours while being subjected to ultrasonic energy. After etching the single wall carbon nanotube bundles etched for 20 hours had an average length of 4 μm and the single wall carbon nanotube bundles etched for 24 hours had an average bundle length of 0.5 μm, as shown by the transmission electron microscopy images in FIGS. 1B -1C. Alternatively, the purified materials can be chemically functionalized by, for example, chemically or physically attaching chemical species to the outer surfaces of the carbon nanotubes such that they will be either soluble or form stable suspensions in certain solvents.
- According to another alternative, the purified raw material can be shortened by mechanical milling. According to this technique, a sample of the purified carbon nanotube material is placed inside a suitable container, along with appropriate milling media. The container is then shut and placed within a suitable holder of a ball-milling machine. According to the present invention, the time that the sample is milled can vary. An appropriate amount of milling time can be readily determined by inspection of the milled nanotubes.
- Regardless of the technique utilized, the preferred length of the shortened material, such as the above-mentioned nanotubes and nanotube bundles, is approximately 0.1-100 micrometers, preferably 0.1-10 micrometers, and more preferably 0.3-3.0 micormeters.
- The purified raw material, regardless of whether subjected to the above-described shortening process, can also optionally be annealed at a suitable temperature, such as 100° C.-1200° C. According to a preferred embodiment, the annealing temperature is 100° C.-600° C. The material is annealed for a suitable time period, such as approximately 1 to 60 minutes. According to a preferred embodiment, the material is annealed for approximately 1 hour. The material is annealed in a vacuum of about 10−2 torr, or at an even higher vacuum pressure. According to a preferred embodiment, the vacuum is about 5×10−7 torr.
- The above described “raw” or pre-formed material can now be introduced into a solution for deposition onto a substrate.
- A suitable liquid medium is selected which will permit the formation of a stable suspension of the raw nanostructure material therein. According to a preferred embodiment the liquid medium comprises at least one of water, methanol, ethanol, alcohol, and dimethylformamide (DMF). According to a further preferred embodiment, the liquid medium comprises ethanol. Upon adding the raw material to the liquid medium, the mixture can optionally be subjected to ultrasonic energy or stirring using, for example, a magnetic stirrer bar, in order to facilitate the formation of a stable suspension. The amount of time that the ultrasonic energy is applied can vary, but it has been found that approximately two hours at room temperature is sufficient.
- The concentration of raw material in the liquid medium can be varied, so long as a stable suspension is formed. For example, with a liquid medium comprising methanol, approximately 0.01 mg of the raw material, such as single-walled carbon nanotubes, can be present per ml of the liquid medium (0.01 mg/ml) and provide a stable suspension. When the liquid medium comprises DMF, approximately 0.4-0.5 mg of the raw material, such as single-walled carbon nanotubes, can be present per ml of the liquid medium (0.4-0.5 mg/ml) and provide a stable suspension. When shortened carbon nanotubes are used, stable suspension can be obtained at a higher concentration. For example, a stable dispersion of approximately 0.1 mg/ml of shortened nanotubes in water can be formed.
- According to a preferred embodiment, a “charger” is added to the suspension in order to facilitate electrophoretic deposition. One such preferred charger is MgCl2. Some other chargers include Mg(NO3)2, La(NO3)3, Y(NO3)3, AlCl3, and sodium hydroxide. Any suitable amount can be utilized. Amounts ranging from less than 1% up to 50%, by weight, as measured relative top to the amount of nanostructure-containing material, are feasible. According to a preferred embodiment, the suspension can contain less than 1% of the charger.
- A plurality of electrodes are then introduced into the suspension. According to a preferred embodiment, two electrodes are utilized. One of the electrodes comprises the substrate upon which the nanostructure material is to be deposited. Any suitable substrate material is envisioned, so long as it possesses `the requisite degree of electrical conductivity. According to a preferred embodiment, the substrate is either metal or doped silicon.
- An alternating current, or a direct current is applied to the electrodes thereby producing an electrical field between the electrodes. This causes the nanotstructure material in the suspension to migrate toward and attach to the substrate electrode. According to one embodiment, the electrical field applied between electrodes is 0.1-1000 V/cm, and a direct current of 0.1-200 mA/cm2 is applied for 1 second-1 hour.
- FIG. 2 is a schematic illustration of the above-described process. As illustrated in FIG. 2, a pair of electrodes E1 and E2 are introduced into the suspension Ssusp. The electrodes E1 and E2 are connected to a power supply P, which produces an electrical field between E1 and E2. Depending on the charge of the nanostructure material contained in the suspension Ssusp, the nanostructure material will migrate toward and attach to one of the electrodes thereby forming a coating C of the nanostructure material on one of the electrodes. In the illustrative example, the substrate Ssub is the negative electrode E1, or anode.
- According to a preferred embodiment, the above-described electrophoretic deposition is carried out at room temperature.
- The rate of deposition of the coating C, as well as its structure and morphology can be influenced by many factors. Such factors include: the concentration of nanostructure material in the suspension Ssusp, the concentration of the charger material (e.g. —MgCl2) in the suspension Ssusp, the conductivity of the substrate, and control of the power source P.
- By way of illustration, a stainless steel substrate/electrode and a counter electrode were introduced into a suspension comprising DMF and single-walled carbon nanotubes at a concentration of 0.4 mg/ml, and MgCl2. A direct current was applied resulting in an electrical field of approximately 20 V/cm formed between the electrodes. Application of the current for about 30 seconds results in the formation of a smooth film of single-walled carbon nanotubes on the substrate. After application of direct current for approximately 10 minutes, a thin film of single-walled carbon nanotubes approximately 1 micrometer thick was deposited on the substrate. This film was examined using a scanning electron microscope, and is illustrated in FIG. 3A. The morphology of the deposited coating or film is similar to that of coating or film applied by spraying, and comprises clearly defined single-walled carbon nanotube bundles.
- FIG. 3B is a SEM image of a coating of single-walled carbon nanotube bundles deposited by electrophoretic deposition in the manner described above. However, the nanotubes were subjected to a previously described process to shorten their length (e.g.—to about a 0.5μm average bundle length). The film depicted in FIG. 3 was densified by sintering in vacuum at a suitable temperature (e.g.—800° C.). This coating comprises distinct grain boundaries with densely packed grains. Individual single-walled carbon nanotube bundles are no longer discernable.
- The particular electrode (i.e.—anode or the cathode) to which the nanostructure material migrates can be controlled through the selection of the charger material. For example, the use of a “negative” charger, such as sodium hydroxide (NaOH) imparts a negative charge to the nanostructure material, thereby creating a tendency for the nanostructure material to migrate towards the positive electrode (cathode). Conversely, when a “positive” charger material is used, such as MgCl2, a positive charge is imparted to the nanostructure material, thereby creating a tendency for the nanostructure material to migrate toward the negative electrode (anode).
- The electrodes are removed from the suspension after a suitable deposition period. The coated substrate electrode may optionally be subjected to further processing. For example, the coated substrate may be annealed to remove the liquid medium. Such an annealing procedure may be preferable, since removal of impurities such as residual suspension medium improves the emission characteristics of the nanostructure material. By way of example, the coated substrate can be heated to a temperature of approximately 100-1200° C. for approximately 1 hour, and then at approximately 800° C. for 2 hours, both at a vacuum of approximately 5×10−7 torr.
- The emission characteristics of a film of single-walled carbon nanotubes (SWNT) formed according to the present invention has been evaluated and compared to that of SWNT materials prepared by other techniques. The results are summarized in following table.
- In the following table, the measurements were made using a constant DC voltage. The threshold field is defined as the electrical field required for the emission current density to reach 0.01 mA/cm2. The current decay is calculated by (Iinitial-Ifinal)/Iinitial, where Iinitial is the initial emission current and Ifinal is the emission current after 10 h of measurement.
Initial emission Emission current Threshold field current density decay after 10 hours Materials [V/micrometer] [mA/cm2] [%] As-grown SWNT 1.3 200 50 mat Purified SWNT 1.0 93 40 paper (made by filtration) CVD SWNT film 3.1 10 79 [a] EPD long SWNT 1.4 83 3 film - FIG. 4 is a plot of the total electron field emission current versus applied voltage for two samples of nanotube films A and B. Sample A was formed as previously described, using methanol as a suspension media. Sample B was formed using DMF as a suspension media. For both samples, the measurements were made over a 6 mm2 emissions area at a cathode-anode distance of 160 μm at a base pressure of 2×10−7 torr. The inset portion of FIG. 4 represents the same data plotted as I/V2 versus I/V, which shows a substantially linear behavior which is indicative of field emission of electrons.
- According to the present invention, a film is formed having a threshold field for emission of less than 1.5 volts/micrometer. The film can produce an emission current density greater than 1 A/cm2. The film can produce a total emission current greater than 10 mA over a 6 mm2 area. The film can also produce a pulsed emission current having a pulse frequency higher than 10 KHz, preferably higher than 100 KHz. The total pulsed current measured over a 6 mm2 area is preferably higher than 10 mA at 10-12 V/μm. Moreover, the emission current is capable of being consistently reproduced, without decay, even after a number of pulsed emissions, as evidenced by the above data. For instance, the pulsed current is stable and higher than 10 mA over a 6 mm2 area for at least 1,000 pulses, preferably for at least 10,000 pulses.
- As apparent from the above, the single-walled carbon nanotube film formed according to the principles of the present invention exhibit excellent field emission characteristics, especially in the area of resistance to emission current density decay.
- The coating of nanostructure materials deposited according to the principles of the present invention exhibit better adhesion that a similar coatings applied by other techniques such as spraying. While not wishing to be limited by any particular theory, the improved adhesion may be due to the formation of metal hydroxide on the surface of the substrate (formed from metal ions of the electrode and OH groups from the charger). The films formed according to the principles of the present invention also exhibit improved field emission stability (i.e.—higher resistance to field emission decay).
- According to a further embodiment, the adhesion of nanotubes to the substrate can be further improved by incorporation of adhesion promoting materials such as binders, carbon-dissolving or carbide-forming metal and high temperature annealing. These materials can be introduced by, for example, one of the following processes: co-deposition of the nanostructures and particles of adhesion promoting materials, sequential deposition, pre-deposition of a layer of adhesion promoting materials, etc.
- In one embodiment, binders such as polymer binders are added to the suspension of the nanostructure-containing material which is then either stirred or sonicated to obtain a uniform suspension. Suitable polymer binders include poly(vinyl butyral-co vinyl alcohol-co-vinyl acetate) and poly(vinylidene fluoride). Suitable chargers are chosen such that under the applied electrical field, either DC or AC, the binder and the nanostructures would migrate to the same electrodes to form a coating with an intimate mixing of the nanostructures and the binder.
- In another embodiment, small metal particles such as titanium, iron, lead, tin, cobalt are mixed into the suspension of the nanostructure-containing material. Suitable chargers are chosen such that under the applied electrical field, the metal particles and the nanostructures will migrate to the desired electrode to form a uniform coating with an intimate mixing of the metal particles and the nanostructures. After deposition, the coated substrate is annealed in vacuum with a base vacuum pressure of 10−3 torr or greater for 0.1-10 hours. Preferably, the diameter of the particles is smaller than 1 micrometer.
- The binders or adhesion promoting materials can be added in any suitable amount. Amounts ranging from 0.1-20% by weight, measured relative to the amount of nanostructure-containing material is envisioned.
- In another embodiment, the substrate to be coated with the nanostructures is first coated with at least one layer of adhesion-promoting metal such as titanium, iron, lead, tin, cobalt, nickel, tantalum, tungsten, niobium, zirconium, vanadium, chromium or hafnium. The layer can be applied by techniques such as electrochemical plating, thermal evaporation, sputtering or pulsed laser deposition. After electrophoretic deposition of the nanostructures, the film is annealed in vacuum with a base vacuum pressure of 10−3 torr or greater for 0.1-10 hours.
- Thus, the above-described processes are advantageously well-adapted for high output and automation. These processes are very versatile and can be used to form uniform coatings of various thicknesses (e.g.—tens of nanometers to a few micrometers thick), coatings on complex shapes, as well as complicated structures such as composites and “gated” electrodes. The methods of the present invention are useful in producing nanotube materials which have properties that make them beneficial for use in a number of different applications. Generally, the method of the present invention is especially beneficial in providing nanotube material for incorporation into electron field emission cathodes for devices such as x-ray generating devices, gas discharge tubes, lighting devices, microwave power amplifiers, ion guns, electron beam lithography devices, high energy accelerators, free electron lasers, electron microscopes and microprobes, and flat panel displays.
- The electrophoresis method of the present invention can used to coat substrates with composite layers in which nanostructured materials serve as one of the components. It can also be utilized to form multilayered structures on a supporting surface.
- To deposit a composite layer containing nanostructure-containing material on a substrate, nanostructured materials and at least one more component (e.g. —polymer or metal particles) are suspended in a liquid medium to make up the electrophoresis bath. After selectively adding a “charger” to the suspension, two electrodes, wherein at least one of the electrodes comprises the substrate, are immersed in the suspension and a direct or alternating current is applied to the immersed electrodes thereby creating an electrical field between the electrodes. Because the nanostructured materials and the other component in the suspension are charged by the same “charger”, they would migrate toward and attach to the same substrate simultaneously under the same electrical field. In the above described method, the composition of deposited composite layer is mostly decided by the composition of the suspension in which the electrophoresis has been carried out. Therefore, composite layers having different composition can be readily obtained by immersing a substrate in baths with deferent compositions and performing the above-described electrophoretic deposition.
- While a composite layer can be made by electrophoresis using only one bath, multiple baths can be used to produce a multilayered electrophoretic deposition. The electrophoresis is carried out in each bath sequentially with each bath producing a layer of different composition in the multilayered structure. When the desired thickness of a layer is reached, the deposition electrode can be moved to the next suspension for deposition of the next layer.
- The electrophoretic deposition technique disclosed can be further applied to deposit an individual or a bundle of carbon nanotubes or nanowires selectively onto a sharp tip. This sharp tip can be, for example, the tip used for microscopes including atomic force microscopes, scanning tunneling microscopes, or profilometers.
- One such embodiment is illustrated in FIGS.5A-5B, where a dilute suspension of nanotube or nanowire is first prepared. A
counter electrode 510 is first immersed into thesuspension 520. Themetal tip 530 is used as the second electrode. It is first placed perpendicular to the suspension surface with the sharp tip, where the nanotube/nanowire is to be deposited, just slightly above the top surface of the suspension. The tip is then gradually moved towards the surface of the suspension. A meter such as acurrent meter 540 is used to monitor the electrical current between the counter electrode and the metal tip. In addition, an appropriate optical magnification device can be used to monitor the gap between themetal tip 530 and thesuspension surface 520. When the tip touches the surface of the suspension, the electrical current passing between the two electrodes is detected by themeter 540. Depending on the concentration of the nanostructures in the suspension and the electrical field used, thetip 530 is allowed to stay in contact with for a pre-determined time. The voltage applied between the two electrodes is then turned off and thetip 530 is raised to be above the suspension to stop the deposition process. Themetal tip 530 with acarbon nanotube 550 or other nanostructure attached to is vacuum annealed to increase the bonding between the tip and the nanostructure. FIG. 5C is an SEM image of a sharp tip having a single nanotube or nanowire deposited thereon according to the techniques of the present invention. - Another application of the process of the present invention is fabrication of triode-type structures with nanostructured field emission materials deposited in selected areas. Such structures can be used, for example, in field emission flat panel displays; cold cathodes for x-ray tubes, microwave amplifiers, etc.
- In one embodiment of this application is illustrated in FIGS.6A-7B, where a multilayer structure comprising a
Si substrate 610, a dielectric insulatinglayer 620 such as silicon dioxide, aconducting layer 630 and a layer ofphotoresist 640 is fabricated by common thin film fabrication techniques (FIG. 6A). A photo-mask is used to selectively expose thephotoresist 640 to ultraviolet light. The multilayer structure is then developed using suitable chemicals to remove the exposed underlying multi-layer structure at the desired locations (FIG. 6B). As illustrated in FIG. 6B, the dimension D of the exposed areas ofsubstrate 610 is small. For example, D can be on the order of 1-100 micrometers, preferably 5-20 micrometers. The exposed areas can be in the form of an array of rounded holes or polygons such as squares. As illustrated in FIG. 6C, carbon nanotubes or other nanostructures are selectively deposited on the exposed Si surfaces ofsubstrate 610 by electrophoresis. In one embodiment, the chemical etched structure is immersed into a carbon nanotube suspension. Contact to the power source is made on the back ofsurface 610. A metal plate is used as the counter electrode. A bias voltage is also preferably applied to theconductive surface 630 to prevent deposition of carbon nanotubes on the metal surface. Under the applied electrical field, carbon nanotubes will migrate to the exposed surfaces ofsubstrate 610. - For purposes of illustration, the
dielectric layer 620 can have a thickness on the order of 1-100 micrometers, preferably 1-10 micrometers. - FIG. 7A and 7B show the top view of the etched multi-layer structures formed as described above.
- In addition, the electrophoresis method of the present invention can also be utilized to form a patterned deposit of nanostructure-containing material onto a substrate.
- FIGS. 8A to8D illustrate one embodiment of this application. According to the illustrated embodiment, a
mask 640 is placed on top of a first surface of asubstrate 650 before electrophoresis. Thearea 670 on the surface ofsubstrate 650 where no deposition is intended is blocked by themask 640, while theareas 660 on the surface ofsubstrate 650 are exposed to the electrophoresis bath through corresponding openings in themask 640. - The masked substrate is then introduced into a suspension and coated by electrophoresis in a manner consistent with the present invention, as set forth in detail above.
- After deposition, the
mask 640 is removed from thesubstrate 650 and a clean patternedstructures 680 containing nanostructure-containing material is obtained, as illustrated in FIG. 8D. The dimension(s) and shape(s) of the patterned structures are defined by the openings of themask 640. - FIGS. 8A and 8B show the side and the top view of the mask-blocked substrate before electrophoresis. FIG. 8C shows the side view of the mask-blocked substrate after electrophoresis. FIG. 8D is the side view of the final structures on the substrate.
- While the present invention has been described by reference to the above-mentioned embodiments, certain modifications and variations will be evident to those of ordinary skill in the art. Therefore, the present invention is limited only by the scope and spirit of the appended claims.
Claims (73)
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Cited By (83)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020063126A1 (en) * | 2000-11-30 | 2002-05-30 | Kim Dae Sik | Heating apparatus of microwave oven |
US20040055420A1 (en) * | 2002-05-30 | 2004-03-25 | Arkady Garbar | Method for enhancing surface area of bulk metals |
US20040055892A1 (en) * | 2001-11-30 | 2004-03-25 | University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US20040211271A1 (en) * | 2003-04-24 | 2004-10-28 | Han Chang Soo | Method for attaching rod-shaped nano structure to probe holder |
US20040239234A1 (en) * | 2001-03-19 | 2004-12-02 | Per Andersson | Microfluidic system |
US20040241896A1 (en) * | 2003-03-21 | 2004-12-02 | The University Of North Carolina At Chapel Hill | Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles |
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US20050112048A1 (en) * | 2003-11-25 | 2005-05-26 | Loucas Tsakalakos | Elongated nano-structures and related devices |
US20050133372A1 (en) * | 2001-11-30 | 2005-06-23 | The University Of North Carolina | Method and apparatus for attaching nanostructure-containing material onto a sharp tip of an object and related articles |
US20050150767A1 (en) * | 2004-01-14 | 2005-07-14 | Industrial Technology Research Institute | Method for assembling carbon nanotubes and microprobe and an apparatus thereof |
WO2005065218A2 (en) * | 2003-12-24 | 2005-07-21 | Xintek, Inc. | Method of synthesizing small-diameter carbon nanotubes with electron field emission properties |
WO2005046305A3 (en) * | 2003-11-06 | 2005-07-28 | Brian Ruby | Method of producing nanostructure tips |
US20050170177A1 (en) * | 2004-01-29 | 2005-08-04 | Crawford Julian S. | Conductive filament |
US20050181195A1 (en) * | 2003-04-28 | 2005-08-18 | Nanosys, Inc. | Super-hydrophobic surfaces, methods of their construction and uses therefor |
US20050263456A1 (en) * | 2003-03-07 | 2005-12-01 | Cooper Christopher H | Nanomesh article and method of using the same for purifying fluids |
US20050271808A1 (en) * | 2004-03-25 | 2005-12-08 | Nomadics, Inc. | Process and apparatus for layer by layer assembly of reinforced composite materials |
US20060008047A1 (en) * | 2000-10-06 | 2006-01-12 | The University Of North Carolina At Chapel Hill | Computed tomography system for imaging of human and small animal |
WO2006008736A1 (en) * | 2004-07-22 | 2006-01-26 | Cerel (Ceramic Technologies) Ltd. | Fabrication of electrical components and circuits by selective electrophoretic deposition (s-epd) and transfer |
US20060049736A1 (en) * | 2004-09-03 | 2006-03-09 | Chun-Yen Hsiao | Method and structure of converging electron-emission source of field-emission display |
US20060076238A1 (en) * | 2001-06-14 | 2006-04-13 | Hyperion Catalysis International, Inc. | Field emission devices using ion bombarded carbon nanotubes |
US20060093750A1 (en) * | 2004-10-28 | 2006-05-04 | Bang Woo Han | Method for patterning nano-sized structure |
US20060213774A1 (en) * | 2005-03-28 | 2006-09-28 | Teco Nanotech Co., Ltd. | Method for enhancing homogeneity and effeciency of carbon nanotube electron emission source of field emission display |
US20060217025A1 (en) * | 2005-03-28 | 2006-09-28 | Teco Nanotech Co., Ltd. | Method for enhancing homogeneity of carbon nanotube electron emission source made by electrophoresis deposition |
US20060249388A1 (en) * | 2005-05-04 | 2006-11-09 | Yu-Yang Chang | Electrophoretic deposition method for a field emission device |
US20070000782A1 (en) * | 2005-06-29 | 2007-01-04 | Teco Electric & Machinery Co., Ltd. | Method for batch fabricating electron emission source of electrophoresis deposited carbon nanotubes |
US20070014148A1 (en) * | 2004-05-10 | 2007-01-18 | The University Of North Carolina At Chapel Hill | Methods and systems for attaching a magnetic nanowire to an object and apparatuses formed therefrom |
US20070053489A1 (en) * | 2005-04-25 | 2007-03-08 | The University Of North Carolina At Chapel Hill | X-ray imaging systems and methods using temporal digital signal processing for reducing noise and for obtaining multiple images simultaneously |
US7211320B1 (en) | 2003-03-07 | 2007-05-01 | Seldon Technologies, Llc | Purification of fluids with nanomaterials |
US20070095665A1 (en) * | 2005-11-03 | 2007-05-03 | Teco Electric & Machinery Co., Ltd. | Method for enhancing life span and adhesion of electrophoresis deposited electron emission source |
WO2007053155A2 (en) * | 2004-11-24 | 2007-05-10 | The Regents Of The University Of California | High power density supercapacitors with carbon nanotube electrodes |
US7220971B1 (en) | 2004-12-29 | 2007-05-22 | The University Of North Carolina At Chapel Hill | Multi-pixel electron microbeam irradiator systems and methods for selectively irradiating predetermined locations |
US7224039B1 (en) * | 2003-09-09 | 2007-05-29 | International Technology Center | Polymer nanocomposite structures for integrated circuits |
US20070187246A1 (en) * | 2006-02-16 | 2007-08-16 | Teco Electric & Machinery Co., Ltd. | Method of manufacturing carbon nanotube electron field emitters by dot-matrix sequential electrophoretic deposition |
US20070187245A1 (en) * | 2006-02-16 | 2007-08-16 | Teco Electric & Machinery Co., Ltd. | Method for fabricating nanotube electron emission source by scanning-matrix type electrophoresis deposition |
US20070199826A1 (en) * | 2006-02-28 | 2007-08-30 | Korea Advanced Institute Of Science And Technology | Method for manufacturing metal/carbon nanotube nano-composite using electroplating |
WO2007101906A1 (en) * | 2006-03-08 | 2007-09-13 | Canatu Oy | Method for depositing high aspect ratio molecular structures |
US20070215473A1 (en) * | 2006-03-17 | 2007-09-20 | Teco Electric & Machinery Co., Ltd. | Method for sequentially electrophoresis depositing carbon nanotube of field emission display |
US20070243717A1 (en) * | 2004-11-29 | 2007-10-18 | Francisco Santiago | Carbon nanotube apparatus and method of carbon nanotube modification |
US20070240988A1 (en) * | 2006-04-17 | 2007-10-18 | Teco Electric & Machinery Co., Ltd. | Method for controlling concentration of electrophoresis solution of carbon nano tube |
US7300860B2 (en) * | 2004-03-30 | 2007-11-27 | Intel Corporation | Integrated circuit with metal layer having carbon nanotubes and methods of making same |
US20080069420A1 (en) * | 2006-05-19 | 2008-03-20 | Jian Zhang | Methods, systems, and computer porgram products for binary multiplexing x-ray radiography |
US7381316B1 (en) * | 2002-04-30 | 2008-06-03 | Northwestern University | Methods and related systems for carbon nanotube deposition |
US7422667B1 (en) * | 2001-04-17 | 2008-09-09 | University Of Central Florida Research Foundation, Inc. | Electrochemical deposition of carbon nanoparticles from organic solutions |
DE102007012550A1 (en) * | 2007-03-13 | 2008-09-25 | Sineurope Nanotech Gmbh | Deposition of nanoparticles uses electrode mounted on transparent substrate, on to which nanoparticles are electrophoretically deposited, electrode being made from conductive material which can be electrochemically converted to insulator |
US20080286521A1 (en) * | 2005-06-13 | 2008-11-20 | Dietmar C Eberlein | System and Method for the Manipulation, Classification Sorting, Purification, Placement, and Alignment of Nano Fibers Using Electrostatic Forces And Electrographic Techniques |
CN100437881C (en) * | 2005-03-14 | 2008-11-26 | 东元奈米应材股份有限公司 | Method of inproving nano-carbon tube electronic emitting performance of field emitting display |
US20080317631A1 (en) * | 2007-06-20 | 2008-12-25 | Reginald Conway Farrow | Nanotube Device and Method of Fabrication |
US20080315302A1 (en) * | 2007-06-20 | 2008-12-25 | Reginald Conway Farrow | Method of Forming Nanotube Vertical Field Effect Transistor |
US20090022264A1 (en) * | 2007-07-19 | 2009-01-22 | Zhou Otto Z | Stationary x-ray digital breast tomosynthesis systems and related methods |
US20090134772A1 (en) * | 2007-11-23 | 2009-05-28 | Tsinghua University | Color field emission display having carbon nanotubes |
US20090169996A1 (en) * | 2008-01-02 | 2009-07-02 | Aruna Zhamu | Hybrid nano-filament anode compositions for lithium ion batteries |
WO2010001125A2 (en) * | 2008-07-03 | 2010-01-07 | Ucl Business Plc | Method for separating nanomaterials |
US20100028543A1 (en) * | 2007-10-30 | 2010-02-04 | Auburn University | Inorganic Nanocylinders in Liquid Crystalline Form |
WO2010017546A1 (en) * | 2008-08-08 | 2010-02-11 | William Marsh Rice University | Carbon nanotube based magnetic resonance imaging contrast agents |
US20100098877A1 (en) * | 2003-03-07 | 2010-04-22 | Cooper Christopher H | Large scale manufacturing of nanostructured material |
US20100140562A1 (en) * | 2003-09-09 | 2010-06-10 | Olga Shenderova | Nano-carbon hybrid structures |
CN101837951A (en) * | 2010-05-24 | 2010-09-22 | 山东大学 | Apparatus and method for graphically producing nano structures by way of electrode induction and microwave curing |
US20100239064A1 (en) * | 2005-04-25 | 2010-09-23 | Unc-Chapel Hill | Methods, systems, and computer program products for multiplexing computed tomography |
US20100279179A1 (en) * | 2007-06-20 | 2010-11-04 | New Jersey Institute Of Technology | System and Method for Directed Self-Assembly Technique for the Creation of Carbon Nanotube Sensors and Bio-Fuel Cells on Single Plane |
US20100329413A1 (en) * | 2009-01-16 | 2010-12-30 | Zhou Otto Z | Compact microbeam radiation therapy systems and methods for cancer treatment and research |
EP2340229A1 (en) * | 2008-10-24 | 2011-07-06 | KME Germany AG & Co. KG | Method for producing a carbon nanotube-, fullerene- and/or graphene-containing coating |
US20110165337A1 (en) * | 2007-05-07 | 2011-07-07 | Nanosys, Inc. | Method and system for printing aligned nanowires and other electrical devices |
US20110163772A1 (en) * | 2008-09-17 | 2011-07-07 | Kim Jung-Yup | Micro contact probe coated with nanostructure and method for manufacturing the same |
CN102169102A (en) * | 2011-01-13 | 2011-08-31 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
US20120086943A1 (en) * | 2009-03-17 | 2012-04-12 | Tokyo Institute Of Technology | Process for producing nanoparticle monolayers |
WO2012117205A1 (en) * | 2011-03-03 | 2012-09-07 | Centre National De La Recherche Scientifique | Method for structuring a surface using colloidal particles in an electric field, resultant surfaces, and uses thereof |
US8358739B2 (en) | 2010-09-03 | 2013-01-22 | The University Of North Carolina At Chapel Hill | Systems and methods for temporal multiplexing X-ray imaging |
FR2981952A1 (en) * | 2011-11-02 | 2013-05-03 | Fabien Gaben | PROCESS FOR MAKING THIN FILMS DENSED BY ELECTROPHORESIS |
US20130153431A1 (en) * | 2005-09-01 | 2013-06-20 | Micron Technology, Inc. | Methods and apparatus for sorting and/or depositing nanotubes |
US8540889B1 (en) | 2008-11-19 | 2013-09-24 | Nanosys, Inc. | Methods of generating liquidphobic surfaces |
US20130302592A1 (en) * | 2012-05-09 | 2013-11-14 | Korea Institute Of Science And Technology | Method for growth of carbon nanoflakes and carbon nanoflake structure |
US20140231265A1 (en) * | 2006-12-05 | 2014-08-21 | Vijay S. Wakharkar | Electronic Packages and Components Thereof Formed by Co-Deposited Carbon Nanotubes |
US20140291296A1 (en) * | 2011-10-12 | 2014-10-02 | The Regents Of The University Of California | Nanomaterials fabricated using spark erosion and other particle fabrication processes |
US20150137371A1 (en) * | 2009-10-01 | 2015-05-21 | Northeastern University | Nanoscale Interconnects Fabricated by Electrical Field Directed Assembly of Nanoelements |
US20150233971A1 (en) * | 2008-02-19 | 2015-08-20 | West Virginia University Research Corporation | Stimulus responsive nanoparticles |
US20150364691A1 (en) * | 2014-06-12 | 2015-12-17 | South University Of Science And Technology Of China | Infrared detector with swnt-based double-cantilever and manufacture thereof |
US9340418B2 (en) | 2008-07-03 | 2016-05-17 | Ucl Business Plc | Method for dispersing and separating nanotubes with an electronic liquid |
US9634251B2 (en) * | 2012-02-27 | 2017-04-25 | Nantero Inc. | Nanotube solution treated with molecular additive, nanotube film having enhanced adhesion property, and methods for forming the nanotube solution and the nanotube film |
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US20220028644A1 (en) * | 2018-11-27 | 2022-01-27 | University-Industry Cooperation Group Of Kyung Hee University | Field emission-type tomosynthesis system, emitter for field emission-type tomosynthesis system, and method of manufacturing emitter |
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Families Citing this family (85)
Publication number | Priority date | Publication date | Assignee | Title |
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US7828619B1 (en) * | 2005-08-05 | 2010-11-09 | Mytitek, Inc. | Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby |
JP4910332B2 (en) * | 2005-08-17 | 2012-04-04 | Nok株式会社 | Method for producing carbon material thin film |
KR100722085B1 (en) * | 2005-09-12 | 2007-05-25 | 삼성전자주식회사 | Photovoltaic cell comprising CNTs formed by using electrophoretic deposition and its fabrication method |
GB0601319D0 (en) | 2006-01-23 | 2006-03-01 | Imp Innovations Ltd | A method of fabricating pillars composed of silicon-based material |
GB0601318D0 (en) | 2006-01-23 | 2006-03-01 | Imp Innovations Ltd | Method of etching a silicon-based material |
KR100753909B1 (en) * | 2006-09-09 | 2007-08-31 | 한국원자력연구원 | Repair method of pitting damage or cracks of metals or alloys by using electrophoretic deposition of nanoparticles |
JP4204641B2 (en) | 2006-11-10 | 2009-01-07 | パナソニック株式会社 | Particle placement apparatus and particle placement method |
CN101192494B (en) * | 2006-11-24 | 2010-09-29 | 清华大学 | Electron emission element preparation method |
US7294560B1 (en) * | 2006-11-28 | 2007-11-13 | Motorola, Inc. | Method of assembling one-dimensional nanostructures |
GB0709165D0 (en) | 2007-05-11 | 2007-06-20 | Nexeon Ltd | A silicon anode for a rechargeable battery |
GB0713896D0 (en) | 2007-07-17 | 2007-08-29 | Nexeon Ltd | Method |
GB0713895D0 (en) | 2007-07-17 | 2007-08-29 | Nexeon Ltd | Production |
GB0713898D0 (en) | 2007-07-17 | 2007-08-29 | Nexeon Ltd | A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries |
DE102007044585A1 (en) * | 2007-09-19 | 2009-04-02 | Süd-Chemie AG | Process for the partial coating of catalytically active components on complex components |
US7850874B2 (en) * | 2007-09-20 | 2010-12-14 | Xintek, Inc. | Methods and devices for electrophoretic deposition of a uniform carbon nanotube composite film |
FR2922125B1 (en) * | 2007-10-11 | 2009-12-04 | Univ Paris Curie | METHOD FOR ATTACHING SLABS OF A LAMELLAR MATERIAL TO AN APPROPRIATE SUBSTRATE |
KR101465255B1 (en) * | 2007-11-06 | 2014-11-26 | 엘지전자 주식회사 | Air conditioner |
US8216441B2 (en) * | 2007-12-10 | 2012-07-10 | Applied Materials, Inc. | Electrophoretic solar cell metallization process and apparatus |
KR100934876B1 (en) * | 2008-01-31 | 2010-01-06 | 성균관대학교산학협력단 | Plating method for liga process |
US7520951B1 (en) | 2008-04-17 | 2009-04-21 | International Business Machines (Ibm) Corporation | Method of transferring nanoparticles to a surface |
US10125052B2 (en) | 2008-05-06 | 2018-11-13 | Massachusetts Institute Of Technology | Method of fabricating electrically conductive aerogels |
US8785881B2 (en) | 2008-05-06 | 2014-07-22 | Massachusetts Institute Of Technology | Method and apparatus for a porous electrospray emitter |
WO2009149467A2 (en) * | 2008-06-06 | 2009-12-10 | University Of Washington | Method and system for concentrating particles from a solution |
GB2464158B (en) | 2008-10-10 | 2011-04-20 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
EP2237050A1 (en) * | 2009-03-31 | 2010-10-06 | Centro de Investigación Cooperativa En Biomateriales ( CIC biomaGUNE) | Apparatus and method for the functionalisation of afm tips |
GB2470056B (en) | 2009-05-07 | 2013-09-11 | Nexeon Ltd | A method of making silicon anode material for rechargeable cells |
GB2470190B (en) | 2009-05-11 | 2011-07-13 | Nexeon Ltd | A binder for lithium ion rechargeable battery cells |
US9853292B2 (en) | 2009-05-11 | 2017-12-26 | Nexeon Limited | Electrode composition for a secondary battery cell |
US8911607B2 (en) * | 2009-07-30 | 2014-12-16 | Empire Technology Development Llc | Electro-deposition of nano-patterns |
US20110052896A1 (en) * | 2009-08-27 | 2011-03-03 | Shrisudersan Jayaraman | Zinc Oxide and Cobalt Oxide Nanostructures and Methods of Making Thereof |
US20110086238A1 (en) * | 2009-10-09 | 2011-04-14 | Shrisudersan Jayaraman | Niobium Nanostructures And Methods Of Making Thereof |
GB201005979D0 (en) | 2010-04-09 | 2010-05-26 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
GB201009519D0 (en) | 2010-06-07 | 2010-07-21 | Nexeon Ltd | An additive for lithium ion rechargeable battery cells |
US8491768B2 (en) * | 2010-06-23 | 2013-07-23 | International Business Machines Corporation | Method of purifying nanoparticles in a colloid |
GB201014706D0 (en) | 2010-09-03 | 2010-10-20 | Nexeon Ltd | Porous electroactive material |
GB201014707D0 (en) | 2010-09-03 | 2010-10-20 | Nexeon Ltd | Electroactive material |
EP2641272B1 (en) * | 2010-11-15 | 2019-05-15 | The Government of the United States of America as represented by the Secretary of the Navy | Structure comprising a perforated contact electrode on vertical nanowire array, sensor, method of preparation and method of sensing |
US9145618B2 (en) * | 2010-11-29 | 2015-09-29 | Northeastern University | High rate electric field driven nanoelement assembly on an insulated surface |
CN102180463A (en) * | 2011-02-21 | 2011-09-14 | 电子科技大学 | Method for reducing sheet resistance of graphene thin film |
US10308377B2 (en) | 2011-05-03 | 2019-06-04 | Massachusetts Institute Of Technology | Propellant tank and loading for electrospray thruster |
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FR2982083B1 (en) * | 2011-11-02 | 2014-06-27 | Fabien Gaben | METHOD FOR PRODUCING SOLID ELECTROLYTE THIN FILMS FOR LITHIUM ION BATTERIES |
CN102403175A (en) * | 2011-11-04 | 2012-04-04 | 上海交通大学 | Method for depositing medium barrier layer on micro-nano electrode |
WO2013072687A2 (en) | 2011-11-16 | 2013-05-23 | Nanoridge Materials, Incorporated | Conductive metal enhanced with conductive nanomaterial |
CN103115238B (en) * | 2011-11-17 | 2015-06-10 | 浙江海洋学院 | Preparation method for depositing graphite lubricant coating with high consistent orientation under electric field induction |
CN102431964B (en) * | 2011-12-15 | 2014-08-13 | 北京石油化工学院 | Method for controllable generation of quantum dots or quantum wires |
US9058954B2 (en) | 2012-02-20 | 2015-06-16 | Georgia Tech Research Corporation | Carbon nanotube field emission devices and methods of making same |
CN103455179A (en) * | 2012-05-28 | 2013-12-18 | 东元奈米应材股份有限公司 | High-resolution laser etching method for transparent conducting layer of touch panel |
DE102012208932A1 (en) | 2012-05-29 | 2013-12-05 | Osram Opto Semiconductors Gmbh | Method for producing a component and device for producing a component |
US20150322589A1 (en) * | 2012-06-29 | 2015-11-12 | Northeastern University | Three-Dimensional Crystalline, Homogenous, and Hybrid Nanostructures Fabricated by Electric Field Directed Assembly of Nanoelements |
US9669416B2 (en) * | 2013-05-28 | 2017-06-06 | Massachusetts Institute Of Technology | Electrospraying systems and associated methods |
CN103456581B (en) * | 2013-09-10 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Carbon nanotube field emission cathode and preparation method thereof |
CN103643281B (en) * | 2013-11-14 | 2016-10-05 | 南京康众光电科技有限公司 | The preparation method of electrophoretic deposition carbon nanotube field emitter in a kind of aqueous solution |
DE102014100542A1 (en) * | 2014-01-20 | 2015-07-23 | Osram Opto Semiconductors Gmbh | Method for producing a laterally structured layer and optoelectronic semiconductor component with such a layer |
CN104217907A (en) * | 2014-09-12 | 2014-12-17 | 中国科学院深圳先进技术研究院 | Preparation method for graphene field emitting cathode, and graphene field emitting cathode |
US10980494B2 (en) | 2014-10-20 | 2021-04-20 | The University Of North Carolina At Chapel Hill | Systems and related methods for stationary digital chest tomosynthesis (s-DCT) imaging |
CN104591798B (en) * | 2014-12-29 | 2016-08-24 | 西北工业大学 | The preparation method of electrophoretic deposition nano wire Strengthening and Toughening SiC ORC |
WO2017024444A1 (en) * | 2015-08-07 | 2017-02-16 | Hewlett-Packard Development Company, L.P. | Coating conductive components |
CN105350054B (en) * | 2015-11-25 | 2017-12-08 | 哈尔滨工业大学 | A kind of method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition |
CN106086997A (en) * | 2016-06-17 | 2016-11-09 | 中国科学院金属研究所 | A kind of thermally grown Al2o3or Cr2o3membranous type M Cr Al nano-composite plate and preparation and application |
CN106563176B (en) * | 2016-10-14 | 2019-04-30 | 湖北大学 | A kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating |
US10746686B2 (en) | 2016-11-03 | 2020-08-18 | King Abdulaziz University | Electrochemical cell and a method of using the same for detecting bisphenol-A |
US11499248B2 (en) * | 2017-03-15 | 2022-11-15 | Lawrence Livermore National Security, Llc | Electric field driven assembly of ordered nanocrystal superlattices |
US10141855B2 (en) | 2017-04-12 | 2018-11-27 | Accion Systems, Inc. | System and method for power conversion |
WO2018213867A1 (en) | 2017-05-25 | 2018-11-29 | Micro-X Limited | Device for producing radio frequency modulated x-ray radiation |
US11369929B2 (en) * | 2017-06-22 | 2022-06-28 | University Of Maryland, College Park | Nanoparticles and systems and methods for synthesizing nanoparticles through thermal shock |
CN110400872B (en) * | 2018-04-24 | 2024-02-23 | 中芯国际集成电路制造(天津)有限公司 | Method for manufacturing carbon nano tube storage structure and method for manufacturing semiconductor device |
EP3804472A4 (en) | 2018-05-25 | 2022-03-23 | Micro-X Limited | A device for applying beamforming signal processing to rf modulated x-rays |
US11830735B2 (en) * | 2018-10-03 | 2023-11-28 | Northwestern University | Two-dimensional semiconductor based printable optoelectronic inks, fabricating methods and applications of same |
CN109921679B (en) * | 2019-03-08 | 2020-03-10 | 吉林大学 | Bionic flexible actuator with real-time feedback function and preparation method thereof |
EP3973182A4 (en) | 2019-05-21 | 2023-06-28 | Accion Systems, Inc. | Apparatus for electrospray emission |
KR102217468B1 (en) * | 2019-06-11 | 2021-02-19 | 세메스 주식회사 | Apparatus for dispensing droplet |
JP7267165B2 (en) * | 2019-10-08 | 2023-05-01 | 東海カーボン株式会社 | Carbon nanotube aqueous dispersion, lubricating oil composition, grease composition, and method for producing the same |
EP3933881A1 (en) | 2020-06-30 | 2022-01-05 | VEC Imaging GmbH & Co. KG | X-ray source with multiple grids |
RU2746863C1 (en) * | 2020-07-28 | 2021-04-21 | Сергей Константинович Есаулов | Method for producing composite metal-dispersed coating, dispersed system for precipitation of composite metal-dispersed coating and method for its production |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3037923A (en) * | 1957-12-26 | 1962-06-05 | Sylvania Electric Prod | Process for electrophoretically coating a metal with particulate carbon material |
US5296117A (en) * | 1991-12-11 | 1994-03-22 | Agfa-Gevaert, N.V. | Method for the production of a radiographic screen |
US5795456A (en) * | 1996-02-13 | 1998-08-18 | Engelhard Corporation | Multi-layer non-identical catalyst on metal substrate by electrophoretic deposition |
US5906721A (en) * | 1995-02-01 | 1999-05-25 | Si Diamond Technology, Inc. | Composition and method for preparing phosphor films exhibiting decreased coulombic aging |
US6258237B1 (en) * | 1998-12-30 | 2001-07-10 | Cerd, Ltd. | Electrophoretic diamond coating and compositions for effecting same |
US6319381B1 (en) * | 1998-06-11 | 2001-11-20 | Micron Technology, Inc. | Methods of forming a face plate assembly of a color display |
US6333968B1 (en) * | 2000-05-05 | 2001-12-25 | The United States Of America As Represented By The Secretary Of The Navy | Transmission cathode for X-ray production |
US6342755B1 (en) * | 1999-08-11 | 2002-01-29 | Sony Corporation | Field emission cathodes having an emitting layer comprised of electron emitting particles and insulating particles |
US6456691B2 (en) * | 2000-03-06 | 2002-09-24 | Rigaku Corporation | X-ray generator |
US6462935B1 (en) * | 2001-09-07 | 2002-10-08 | Lih-Ren Shiue | Replaceable flow-through capacitors for removing charged species from liquids |
US20020193040A1 (en) * | 2001-06-18 | 2002-12-19 | Zhou Otto Z. | Method of making nanotube-based material with enhanced electron field emission properties |
US20030111946A1 (en) * | 2001-12-18 | 2003-06-19 | Talin Albert Alec | FED cathode structure using electrophoretic deposition and method of fabrication |
US6616497B1 (en) * | 1999-08-12 | 2003-09-09 | Samsung Sdi Co., Ltd. | Method of manufacturing carbon nanotube field emitter by electrophoretic deposition |
US6652967B2 (en) * | 2001-08-08 | 2003-11-25 | Nanoproducts Corporation | Nano-dispersed powders and methods for their manufacture |
US6824755B2 (en) * | 1996-08-08 | 2004-11-30 | William Marsh Rice University | Method for producing a catalyst support and compositions thereof |
Family Cites Families (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7111360A (en) * | 1971-08-18 | 1973-02-20 | ||
US4500397A (en) * | 1981-07-27 | 1985-02-19 | Sony Corporation | Method for the preparation of a pyroelectric material |
US5956911A (en) * | 1993-02-10 | 1999-09-28 | Kistner Concrete Products, Inc. | Insulated pre-formed wall panels |
JP3381429B2 (en) * | 1994-12-19 | 2003-02-24 | 日本板硝子株式会社 | Method for producing substrate with metal oxide film |
US6057637A (en) * | 1996-09-13 | 2000-05-02 | The Regents Of The University Of California | Field emission electron source |
JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
US6199182B1 (en) * | 1997-03-27 | 2001-03-06 | Texas Instruments Incorporated | Probeless testing of pad buffers on wafer |
EP0971051A1 (en) * | 1998-07-09 | 2000-01-12 | Giacomo Borra | A machine for the electrophoretic re-painting or re-varnishing of thin metal objects |
US6630772B1 (en) * | 1998-09-21 | 2003-10-07 | Agere Systems Inc. | Device comprising carbon nanotube field emitter structure and process for forming device |
EP1054249B1 (en) * | 1998-12-03 | 2007-03-07 | Daiken Chemical Co. Ltd. | Electronic device surface signal control probe and method of manufacturing the probe |
US6280697B1 (en) * | 1999-03-01 | 2001-08-28 | The University Of North Carolina-Chapel Hill | Nanotube-based high energy material and method |
JP3582410B2 (en) * | 1999-07-09 | 2004-10-27 | 松下電器産業株式会社 | Electron emitting device and method of manufacturing the same |
US6462467B1 (en) * | 1999-08-11 | 2002-10-08 | Sony Corporation | Method for depositing a resistive material in a field emission cathode |
US6277318B1 (en) | 1999-08-18 | 2001-08-21 | Agere Systems Guardian Corp. | Method for fabrication of patterned carbon nanotube films |
KR200175925Y1 (en) | 1999-09-30 | 2000-03-15 | 최순자 | Underpants with band fastener |
US6741019B1 (en) * | 1999-10-18 | 2004-05-25 | Agere Systems, Inc. | Article comprising aligned nanowires |
US6401526B1 (en) * | 1999-12-10 | 2002-06-11 | The Board Of Trustees Of The Leland Stanford Junior University | Carbon nanotubes and methods of fabrication thereof using a liquid phase catalyst precursor |
KR100546110B1 (en) | 2000-01-21 | 2006-01-24 | 주식회사 하이닉스반도체 | Photoresist Crosslinking Agent and Photoresist Composition Containing the Same |
JP3730476B2 (en) * | 2000-03-31 | 2006-01-05 | 株式会社東芝 | Field emission cold cathode and manufacturing method thereof |
CA2343873A1 (en) * | 2000-04-12 | 2001-10-12 | Wako Pure Chemical Industries Ltd. | Electrode for dielectrophoretic apparatus, dielectrophoretic apparatus, methdo for manufacturing the same, and method for separating substances using the elctrode or dielectrophoretic apparatus |
JP4579372B2 (en) | 2000-05-01 | 2010-11-10 | パナソニック株式会社 | Electron emitting device, method for manufacturing electron emitting device, and image display device |
CN1128098C (en) | 2000-05-23 | 2003-11-19 | 广东工业大学 | Process for preparing nm-class single-wall carbon tubes by high-power continuous CO2 laser |
US6334939B1 (en) | 2000-06-15 | 2002-01-01 | The University Of North Carolina At Chapel Hill | Nanostructure-based high energy capacity material |
US6420293B1 (en) * | 2000-08-25 | 2002-07-16 | Rensselaer Polytechnic Institute | Ceramic matrix nanocomposites containing carbon nanotubes for enhanced mechanical behavior |
US6457350B1 (en) * | 2000-09-08 | 2002-10-01 | Fei Company | Carbon nanotube probe tip grown on a small probe |
US20030002627A1 (en) * | 2000-09-28 | 2003-01-02 | Oxford Instruments, Inc. | Cold emitter x-ray tube incorporating a nanostructured carbon film electron emitter |
US6553096B1 (en) * | 2000-10-06 | 2003-04-22 | The University Of North Carolina Chapel Hill | X-ray generating mechanism using electron field emission cathode |
US7085351B2 (en) * | 2000-10-06 | 2006-08-01 | University Of North Carolina At Chapel Hill | Method and apparatus for controlling electron beam current |
US6876724B2 (en) * | 2000-10-06 | 2005-04-05 | The University Of North Carolina - Chapel Hill | Large-area individually addressable multi-beam x-ray system and method of forming same |
US7082182B2 (en) * | 2000-10-06 | 2006-07-25 | The University Of North Carolina At Chapel Hill | Computed tomography system for imaging of human and small animal |
US6980627B2 (en) * | 2000-10-06 | 2005-12-27 | Xintek, Inc. | Devices and methods for producing multiple x-ray beams from multiple locations |
US20040240616A1 (en) * | 2003-05-30 | 2004-12-02 | Applied Nanotechnologies, Inc. | Devices and methods for producing multiple X-ray beams from multiple locations |
US7227924B2 (en) * | 2000-10-06 | 2007-06-05 | The University Of North Carolina At Chapel Hill | Computed tomography scanning system and method using a field emission x-ray source |
US6965199B2 (en) * | 2001-03-27 | 2005-11-15 | The University Of North Carolina At Chapel Hill | Coated electrode with enhanced electron emission and ignition characteristics |
JP3536288B2 (en) | 2001-04-05 | 2004-06-07 | 関西ティー・エル・オー株式会社 | Method of manufacturing nanotube probe |
JP2002367543A (en) | 2001-06-12 | 2002-12-20 | Nippon Hoso Kyokai <Nhk> | Field emission display device and its manufacturing method |
WO2002103737A2 (en) * | 2001-06-14 | 2002-12-27 | Hyperion Catalysis International, Inc. | Field emission devices using ion bombarded carbon nanotubes |
US6897603B2 (en) * | 2001-08-24 | 2005-05-24 | Si Diamond Technology, Inc. | Catalyst for carbon nanotube growth |
TW516061B (en) | 2001-09-12 | 2003-01-01 | Ind Tech Res Inst | Manufacturing method for triode-type electron emitting source |
US7455757B2 (en) * | 2001-11-30 | 2008-11-25 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US7252749B2 (en) * | 2001-11-30 | 2007-08-07 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
EP1483202B1 (en) * | 2002-03-04 | 2012-12-12 | William Marsh Rice University | Method for separating single-wall carbon nanotubes and compositions thereof |
US7147894B2 (en) * | 2002-03-25 | 2006-12-12 | The University Of North Carolina At Chapel Hill | Method for assembling nano objects |
US6879143B2 (en) * | 2002-04-16 | 2005-04-12 | Motorola, Inc. | Method of selectively aligning and positioning nanometer-scale components using AC fields |
US20030233871A1 (en) * | 2002-05-17 | 2003-12-25 | Eloret Corporation | Multi-walled carbon nanotube scanning probe apparatus having a sharpened tip and method of sharpening for high resolution, high aspect ratio imaging |
CN1998061B (en) * | 2002-07-03 | 2010-08-04 | 新泰科有限公司 | Fabrication and activation processes for nanostructure composite field emission cathodes |
EP1569733A2 (en) * | 2002-12-09 | 2005-09-07 | The University of North Carolina at Chapel Hill | Methods for assembly and sorting of nanostructure-containing materials and related articles |
US20040256975A1 (en) * | 2003-06-19 | 2004-12-23 | Applied Nanotechnologies, Inc. | Electrode and associated devices and methods |
US7129513B2 (en) * | 2004-06-02 | 2006-10-31 | Xintek, Inc. | Field emission ion source based on nanostructure-containing material |
-
2001
- 2001-11-30 US US09/996,695 patent/US7252749B2/en not_active Expired - Lifetime
-
2002
- 2002-11-20 CA CA002468685A patent/CA2468685A1/en not_active Abandoned
- 2002-11-20 CN CNA028277082A patent/CN1617954A/en active Pending
- 2002-11-20 WO PCT/US2002/037184 patent/WO2003075372A2/en active Application Filing
- 2002-11-20 EP EP02807020A patent/EP1474836A4/en not_active Withdrawn
- 2002-11-20 AU AU2002366269A patent/AU2002366269A1/en not_active Abandoned
- 2002-11-20 KR KR10-2004-7008303A patent/KR20040098623A/en not_active Application Discontinuation
- 2002-11-20 JP JP2003573718A patent/JP4563686B2/en not_active Expired - Fee Related
-
2004
- 2004-05-10 US US10/842,357 patent/US7887689B2/en not_active Expired - Fee Related
-
2005
- 2005-11-04 US US11/266,318 patent/US8002958B2/en not_active Expired - Fee Related
-
2007
- 2007-06-11 US US11/811,649 patent/US20080099339A1/en not_active Abandoned
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3037923A (en) * | 1957-12-26 | 1962-06-05 | Sylvania Electric Prod | Process for electrophoretically coating a metal with particulate carbon material |
US5296117A (en) * | 1991-12-11 | 1994-03-22 | Agfa-Gevaert, N.V. | Method for the production of a radiographic screen |
US5906721A (en) * | 1995-02-01 | 1999-05-25 | Si Diamond Technology, Inc. | Composition and method for preparing phosphor films exhibiting decreased coulombic aging |
US5795456A (en) * | 1996-02-13 | 1998-08-18 | Engelhard Corporation | Multi-layer non-identical catalyst on metal substrate by electrophoretic deposition |
US6824755B2 (en) * | 1996-08-08 | 2004-11-30 | William Marsh Rice University | Method for producing a catalyst support and compositions thereof |
US6319381B1 (en) * | 1998-06-11 | 2001-11-20 | Micron Technology, Inc. | Methods of forming a face plate assembly of a color display |
US6258237B1 (en) * | 1998-12-30 | 2001-07-10 | Cerd, Ltd. | Electrophoretic diamond coating and compositions for effecting same |
US6342755B1 (en) * | 1999-08-11 | 2002-01-29 | Sony Corporation | Field emission cathodes having an emitting layer comprised of electron emitting particles and insulating particles |
US6616497B1 (en) * | 1999-08-12 | 2003-09-09 | Samsung Sdi Co., Ltd. | Method of manufacturing carbon nanotube field emitter by electrophoretic deposition |
US6456691B2 (en) * | 2000-03-06 | 2002-09-24 | Rigaku Corporation | X-ray generator |
US6333968B1 (en) * | 2000-05-05 | 2001-12-25 | The United States Of America As Represented By The Secretary Of The Navy | Transmission cathode for X-ray production |
US20020193040A1 (en) * | 2001-06-18 | 2002-12-19 | Zhou Otto Z. | Method of making nanotube-based material with enhanced electron field emission properties |
US6652967B2 (en) * | 2001-08-08 | 2003-11-25 | Nanoproducts Corporation | Nano-dispersed powders and methods for their manufacture |
US6462935B1 (en) * | 2001-09-07 | 2002-10-08 | Lih-Ren Shiue | Replaceable flow-through capacitors for removing charged species from liquids |
US20030111946A1 (en) * | 2001-12-18 | 2003-06-19 | Talin Albert Alec | FED cathode structure using electrophoretic deposition and method of fabrication |
Cited By (154)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070009081A1 (en) * | 2000-10-06 | 2007-01-11 | The University Of North Carolina At Chapel Hill | Computed tomography system for imaging of human and small animal |
US20060008047A1 (en) * | 2000-10-06 | 2006-01-12 | The University Of North Carolina At Chapel Hill | Computed tomography system for imaging of human and small animal |
US7082182B2 (en) | 2000-10-06 | 2006-07-25 | The University Of North Carolina At Chapel Hill | Computed tomography system for imaging of human and small animal |
US20020063126A1 (en) * | 2000-11-30 | 2002-05-30 | Kim Dae Sik | Heating apparatus of microwave oven |
US20040239234A1 (en) * | 2001-03-19 | 2004-12-02 | Per Andersson | Microfluidic system |
US7422667B1 (en) * | 2001-04-17 | 2008-09-09 | University Of Central Florida Research Foundation, Inc. | Electrochemical deposition of carbon nanoparticles from organic solutions |
US20060076238A1 (en) * | 2001-06-14 | 2006-04-13 | Hyperion Catalysis International, Inc. | Field emission devices using ion bombarded carbon nanotubes |
US20080036358A1 (en) * | 2001-06-14 | 2008-02-14 | Hyperion Catalysis International, Inc. | Field Emission Devices Using Ion Bombarded Carbon Nanotubes |
US7585199B2 (en) * | 2001-06-14 | 2009-09-08 | Hyperion Catalysis International, Inc. | Field emission devices using ion bombarded carbon nanotubes |
US20050133372A1 (en) * | 2001-11-30 | 2005-06-23 | The University Of North Carolina | Method and apparatus for attaching nanostructure-containing material onto a sharp tip of an object and related articles |
US20080006534A1 (en) * | 2001-11-30 | 2008-01-10 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US7887689B2 (en) | 2001-11-30 | 2011-02-15 | The University Of North Carolina At Chapel Hill | Method and apparatus for attaching nanostructure-containing material onto a sharp tip of an object and related articles |
US20080099339A1 (en) * | 2001-11-30 | 2008-05-01 | Zhou Otto Z | Deposition method for nanostructure materials |
US8002958B2 (en) | 2001-11-30 | 2011-08-23 | University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US20040055892A1 (en) * | 2001-11-30 | 2004-03-25 | University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US7252749B2 (en) | 2001-11-30 | 2007-08-07 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US7455757B2 (en) | 2001-11-30 | 2008-11-25 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
US7381316B1 (en) * | 2002-04-30 | 2008-06-03 | Northwestern University | Methods and related systems for carbon nanotube deposition |
US20040055420A1 (en) * | 2002-05-30 | 2004-03-25 | Arkady Garbar | Method for enhancing surface area of bulk metals |
US20050263456A1 (en) * | 2003-03-07 | 2005-12-01 | Cooper Christopher H | Nanomesh article and method of using the same for purifying fluids |
US7211320B1 (en) | 2003-03-07 | 2007-05-01 | Seldon Technologies, Llc | Purification of fluids with nanomaterials |
US7419601B2 (en) | 2003-03-07 | 2008-09-02 | Seldon Technologies, Llc | Nanomesh article and method of using the same for purifying fluids |
US20100098877A1 (en) * | 2003-03-07 | 2010-04-22 | Cooper Christopher H | Large scale manufacturing of nanostructured material |
US6969690B2 (en) | 2003-03-21 | 2005-11-29 | The University Of North Carolina At Chapel Hill | Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles |
WO2004083490A3 (en) * | 2003-03-21 | 2005-06-30 | Univ North Carolina | Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles |
EP1618601A2 (en) * | 2003-03-21 | 2006-01-25 | The University of North Carolina at Chapel Hill | Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles |
EP1618601A4 (en) * | 2003-03-21 | 2006-11-08 | Univ North Carolina | Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles |
US20040241896A1 (en) * | 2003-03-21 | 2004-12-02 | The University Of North Carolina At Chapel Hill | Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles |
US20070033992A1 (en) * | 2003-04-24 | 2007-02-15 | Han Chang S | Method for attaching rod-shaped nano structure to probe holder |
US7082683B2 (en) * | 2003-04-24 | 2006-08-01 | Korea Institute Of Machinery & Materials | Method for attaching rod-shaped nano structure to probe holder |
US20040211271A1 (en) * | 2003-04-24 | 2004-10-28 | Han Chang Soo | Method for attaching rod-shaped nano structure to probe holder |
US20050181195A1 (en) * | 2003-04-28 | 2005-08-18 | Nanosys, Inc. | Super-hydrophobic surfaces, methods of their construction and uses therefor |
US7985475B2 (en) | 2003-04-28 | 2011-07-26 | Nanosys, Inc. | Super-hydrophobic surfaces, methods of their construction and uses therefor |
US20040245527A1 (en) * | 2003-05-30 | 2004-12-09 | Kazuhito Tsukagoshi | Terminal and thin-film transistor |
WO2005014889A3 (en) * | 2003-07-10 | 2006-04-20 | Univ North Carolina Chapel Hill | Deposition method for nanostructure materials |
US8308994B1 (en) | 2003-09-09 | 2012-11-13 | International Technology Center | Nano-carbon hybrid structures |
US7224039B1 (en) * | 2003-09-09 | 2007-05-29 | International Technology Center | Polymer nanocomposite structures for integrated circuits |
US8070988B2 (en) | 2003-09-09 | 2011-12-06 | International Technology Center | Nano-carbon hybrid structures |
US20100140562A1 (en) * | 2003-09-09 | 2010-06-10 | Olga Shenderova | Nano-carbon hybrid structures |
WO2005046305A3 (en) * | 2003-11-06 | 2005-07-28 | Brian Ruby | Method of producing nanostructure tips |
US20050112048A1 (en) * | 2003-11-25 | 2005-05-26 | Loucas Tsakalakos | Elongated nano-structures and related devices |
US7618300B2 (en) | 2003-12-24 | 2009-11-17 | Duke University | Method of synthesizing small-diameter carbon nanotubes with electron field emission properties |
WO2005065218A3 (en) * | 2003-12-24 | 2007-04-19 | Xintek Inc | Method of synthesizing small-diameter carbon nanotubes with electron field emission properties |
US20060055303A1 (en) * | 2003-12-24 | 2006-03-16 | Jie Liu | Method of synthesizing small-diameter carbon nanotubes with electron field emission properties |
JP2007533581A (en) * | 2003-12-24 | 2007-11-22 | キンテク インコーポレーテッド | Method for synthesizing small-diameter carbon nanotubes having electron field emission characteristics |
WO2005065218A2 (en) * | 2003-12-24 | 2005-07-21 | Xintek, Inc. | Method of synthesizing small-diameter carbon nanotubes with electron field emission properties |
US20050150767A1 (en) * | 2004-01-14 | 2005-07-14 | Industrial Technology Research Institute | Method for assembling carbon nanotubes and microprobe and an apparatus thereof |
US20050170177A1 (en) * | 2004-01-29 | 2005-08-04 | Crawford Julian S. | Conductive filament |
US20050271808A1 (en) * | 2004-03-25 | 2005-12-08 | Nomadics, Inc. | Process and apparatus for layer by layer assembly of reinforced composite materials |
US7300860B2 (en) * | 2004-03-30 | 2007-11-27 | Intel Corporation | Integrated circuit with metal layer having carbon nanotubes and methods of making same |
US20070014148A1 (en) * | 2004-05-10 | 2007-01-18 | The University Of North Carolina At Chapel Hill | Methods and systems for attaching a magnetic nanowire to an object and apparatuses formed therefrom |
WO2006008736A1 (en) * | 2004-07-22 | 2006-01-26 | Cerel (Ceramic Technologies) Ltd. | Fabrication of electrical components and circuits by selective electrophoretic deposition (s-epd) and transfer |
US20060049736A1 (en) * | 2004-09-03 | 2006-03-09 | Chun-Yen Hsiao | Method and structure of converging electron-emission source of field-emission display |
US20060093750A1 (en) * | 2004-10-28 | 2006-05-04 | Bang Woo Han | Method for patterning nano-sized structure |
WO2007053155A3 (en) * | 2004-11-24 | 2009-04-09 | Univ California | High power density supercapacitors with carbon nanotube electrodes |
US7553341B2 (en) * | 2004-11-24 | 2009-06-30 | The Regents Of The University Of California | High power density supercapacitors with carbon nanotube electrodes |
US20080010796A1 (en) * | 2004-11-24 | 2008-01-17 | Ning Pan | High power density supercapacitors with carbon nanotube electrodes |
WO2007053155A2 (en) * | 2004-11-24 | 2007-05-10 | The Regents Of The University Of California | High power density supercapacitors with carbon nanotube electrodes |
US7597867B1 (en) | 2004-11-29 | 2009-10-06 | The United States Of America As Represented By The Secretary Of The Navy | Method of carbon nanotube modification |
US7348592B2 (en) | 2004-11-29 | 2008-03-25 | The United States Of America As Represented By The Secretary Of The Navy | Carbon nanotube apparatus and method of carbon nanotube modification |
US20070243717A1 (en) * | 2004-11-29 | 2007-10-18 | Francisco Santiago | Carbon nanotube apparatus and method of carbon nanotube modification |
US7745330B1 (en) | 2004-11-29 | 2010-06-29 | The United States Of America As Represented By The Secretary Of The Navy | Method of carbon nanotube modification |
US7678707B1 (en) | 2004-11-29 | 2010-03-16 | The United States Of America As Represented By The Secretary Of The Navy | Method of carbon nanotube modification |
US7220971B1 (en) | 2004-12-29 | 2007-05-22 | The University Of North Carolina At Chapel Hill | Multi-pixel electron microbeam irradiator systems and methods for selectively irradiating predetermined locations |
US20070114434A1 (en) * | 2004-12-29 | 2007-05-24 | The University Of North Carolina At Chapel Hill | Multi-pixel electron microbeam irradiator systems and methods for selectively irradiating predetermined locations |
CN100437881C (en) * | 2005-03-14 | 2008-11-26 | 东元奈米应材股份有限公司 | Method of inproving nano-carbon tube electronic emitting performance of field emitting display |
US20060217025A1 (en) * | 2005-03-28 | 2006-09-28 | Teco Nanotech Co., Ltd. | Method for enhancing homogeneity of carbon nanotube electron emission source made by electrophoresis deposition |
US20060213774A1 (en) * | 2005-03-28 | 2006-09-28 | Teco Nanotech Co., Ltd. | Method for enhancing homogeneity and effeciency of carbon nanotube electron emission source of field emission display |
US20070053489A1 (en) * | 2005-04-25 | 2007-03-08 | The University Of North Carolina At Chapel Hill | X-ray imaging systems and methods using temporal digital signal processing for reducing noise and for obtaining multiple images simultaneously |
US7245692B2 (en) | 2005-04-25 | 2007-07-17 | The University Of North Carolina At Chapel Hill | X-ray imaging systems and methods using temporal digital signal processing for reducing noise and for obtaining multiple images simultaneously |
US20100239064A1 (en) * | 2005-04-25 | 2010-09-23 | Unc-Chapel Hill | Methods, systems, and computer program products for multiplexing computed tomography |
US8155262B2 (en) | 2005-04-25 | 2012-04-10 | The University Of North Carolina At Chapel Hill | Methods, systems, and computer program products for multiplexing computed tomography |
US20060249388A1 (en) * | 2005-05-04 | 2006-11-09 | Yu-Yang Chang | Electrophoretic deposition method for a field emission device |
US20080286521A1 (en) * | 2005-06-13 | 2008-11-20 | Dietmar C Eberlein | System and Method for the Manipulation, Classification Sorting, Purification, Placement, and Alignment of Nano Fibers Using Electrostatic Forces And Electrographic Techniques |
US8066967B2 (en) * | 2005-06-13 | 2011-11-29 | Electrox Corporation | System and method for the manipulation, classification sorting, purification, placement, and alignment of nano fibers using electrostatic forces and electrographic techniques |
US20070000782A1 (en) * | 2005-06-29 | 2007-01-04 | Teco Electric & Machinery Co., Ltd. | Method for batch fabricating electron emission source of electrophoresis deposited carbon nanotubes |
US20130153431A1 (en) * | 2005-09-01 | 2013-06-20 | Micron Technology, Inc. | Methods and apparatus for sorting and/or depositing nanotubes |
US9290857B2 (en) * | 2005-09-01 | 2016-03-22 | Micron Technology, Inc. | Methods and apparatus for sorting and/or depositing nanotubes |
US20070095665A1 (en) * | 2005-11-03 | 2007-05-03 | Teco Electric & Machinery Co., Ltd. | Method for enhancing life span and adhesion of electrophoresis deposited electron emission source |
US20070187246A1 (en) * | 2006-02-16 | 2007-08-16 | Teco Electric & Machinery Co., Ltd. | Method of manufacturing carbon nanotube electron field emitters by dot-matrix sequential electrophoretic deposition |
US20070187245A1 (en) * | 2006-02-16 | 2007-08-16 | Teco Electric & Machinery Co., Ltd. | Method for fabricating nanotube electron emission source by scanning-matrix type electrophoresis deposition |
US20070199826A1 (en) * | 2006-02-28 | 2007-08-30 | Korea Advanced Institute Of Science And Technology | Method for manufacturing metal/carbon nanotube nano-composite using electroplating |
US8951602B2 (en) | 2006-03-08 | 2015-02-10 | Canatu Oy | Method for depositing high aspect ratio molecular structures |
US20090304945A1 (en) * | 2006-03-08 | 2009-12-10 | Canatu Oy | Method for depositing high aspect ratio molecular structures |
US8871295B2 (en) | 2006-03-08 | 2014-10-28 | Canatu Oy | Method for separating high aspect ratio molecular structures |
US9776206B2 (en) | 2006-03-08 | 2017-10-03 | Canatu Oy | Method for depositing high aspect ratio molecular structures |
US20090280238A1 (en) * | 2006-03-08 | 2009-11-12 | Canatu Oy | Method for separating high aspect ratio molecular structures |
WO2007101906A1 (en) * | 2006-03-08 | 2007-09-13 | Canatu Oy | Method for depositing high aspect ratio molecular structures |
US20070215473A1 (en) * | 2006-03-17 | 2007-09-20 | Teco Electric & Machinery Co., Ltd. | Method for sequentially electrophoresis depositing carbon nanotube of field emission display |
US20070240988A1 (en) * | 2006-04-17 | 2007-10-18 | Teco Electric & Machinery Co., Ltd. | Method for controlling concentration of electrophoresis solution of carbon nano tube |
US8189893B2 (en) | 2006-05-19 | 2012-05-29 | The University Of North Carolina At Chapel Hill | Methods, systems, and computer program products for binary multiplexing x-ray radiography |
US20080069420A1 (en) * | 2006-05-19 | 2008-03-20 | Jian Zhang | Methods, systems, and computer porgram products for binary multiplexing x-ray radiography |
US20140231265A1 (en) * | 2006-12-05 | 2014-08-21 | Vijay S. Wakharkar | Electronic Packages and Components Thereof Formed by Co-Deposited Carbon Nanotubes |
DE102007012550B4 (en) * | 2007-03-13 | 2013-10-10 | Sineurop Nanotech Gmbh | Method and device for depositing nanoparticles and optical element |
DE102007012550A1 (en) * | 2007-03-13 | 2008-09-25 | Sineurope Nanotech Gmbh | Deposition of nanoparticles uses electrode mounted on transparent substrate, on to which nanoparticles are electrophoretically deposited, electrode being made from conductive material which can be electrochemically converted to insulator |
US20110165337A1 (en) * | 2007-05-07 | 2011-07-07 | Nanosys, Inc. | Method and system for printing aligned nanowires and other electrical devices |
US20080317631A1 (en) * | 2007-06-20 | 2008-12-25 | Reginald Conway Farrow | Nanotube Device and Method of Fabrication |
JP2010531065A (en) * | 2007-06-20 | 2010-09-16 | ニユージヤージイ・インスチチユート・オブ・テクノロジー | Method for forming nanotube vertical field effect transistor |
US7964143B2 (en) | 2007-06-20 | 2011-06-21 | New Jersey Institute Of Technology | Nanotube device and method of fabrication |
US8546027B2 (en) | 2007-06-20 | 2013-10-01 | New Jersey Institute Of Technology | System and method for directed self-assembly technique for the creation of carbon nanotube sensors and bio-fuel cells on single plane |
US8257566B2 (en) | 2007-06-20 | 2012-09-04 | New Jersey Institute Of Technology | Nanotube device and method of fabrication |
US20100279179A1 (en) * | 2007-06-20 | 2010-11-04 | New Jersey Institute Of Technology | System and Method for Directed Self-Assembly Technique for the Creation of Carbon Nanotube Sensors and Bio-Fuel Cells on Single Plane |
US7736979B2 (en) * | 2007-06-20 | 2010-06-15 | New Jersey Institute Of Technology | Method of forming nanotube vertical field effect transistor |
US20080315302A1 (en) * | 2007-06-20 | 2008-12-25 | Reginald Conway Farrow | Method of Forming Nanotube Vertical Field Effect Transistor |
US20090022264A1 (en) * | 2007-07-19 | 2009-01-22 | Zhou Otto Z | Stationary x-ray digital breast tomosynthesis systems and related methods |
US7751528B2 (en) | 2007-07-19 | 2010-07-06 | The University Of North Carolina | Stationary x-ray digital breast tomosynthesis systems and related methods |
US20100028543A1 (en) * | 2007-10-30 | 2010-02-04 | Auburn University | Inorganic Nanocylinders in Liquid Crystalline Form |
US7863806B2 (en) * | 2007-11-23 | 2011-01-04 | Tsinghua University | Color field emission display having carbon nanotubes |
US8319413B2 (en) | 2007-11-23 | 2012-11-27 | Tsinghua University | Color field emission display having carbon nanotubes |
US20090134772A1 (en) * | 2007-11-23 | 2009-05-28 | Tsinghua University | Color field emission display having carbon nanotubes |
US20110062856A1 (en) * | 2007-11-23 | 2011-03-17 | Tsinghua University | Color field emission display having carbon nanotubes |
US9564629B2 (en) * | 2008-01-02 | 2017-02-07 | Nanotek Instruments, Inc. | Hybrid nano-filament anode compositions for lithium ion batteries |
US20090169996A1 (en) * | 2008-01-02 | 2009-07-02 | Aruna Zhamu | Hybrid nano-filament anode compositions for lithium ion batteries |
US9658251B2 (en) * | 2008-02-19 | 2017-05-23 | West Virginia University | Stimulus responsive nanoparticles |
US20150233971A1 (en) * | 2008-02-19 | 2015-08-20 | West Virginia University Research Corporation | Stimulus responsive nanoparticles |
US9079775B2 (en) | 2008-07-03 | 2015-07-14 | Ucl Business Plc | Method for separating nanomaterials |
WO2010001125A2 (en) * | 2008-07-03 | 2010-01-07 | Ucl Business Plc | Method for separating nanomaterials |
WO2010001125A3 (en) * | 2008-07-03 | 2010-06-03 | Ucl Business Plc | Method for separating nanomaterials |
US9340418B2 (en) | 2008-07-03 | 2016-05-17 | Ucl Business Plc | Method for dispersing and separating nanotubes with an electronic liquid |
CN102083749A (en) * | 2008-07-03 | 2011-06-01 | Ucl商业有限公司 | Method for separating nanomaterials |
WO2010017546A1 (en) * | 2008-08-08 | 2010-02-11 | William Marsh Rice University | Carbon nanotube based magnetic resonance imaging contrast agents |
US8957690B2 (en) * | 2008-09-17 | 2015-02-17 | Korea Institute Of Machinery & Materials | Micro contact probe coated with nanostructure and method for manufacturing the same |
US20110163772A1 (en) * | 2008-09-17 | 2011-07-07 | Kim Jung-Yup | Micro contact probe coated with nanostructure and method for manufacturing the same |
EP2340229A1 (en) * | 2008-10-24 | 2011-07-06 | KME Germany AG & Co. KG | Method for producing a carbon nanotube-, fullerene- and/or graphene-containing coating |
US8540889B1 (en) | 2008-11-19 | 2013-09-24 | Nanosys, Inc. | Methods of generating liquidphobic surfaces |
US20100329413A1 (en) * | 2009-01-16 | 2010-12-30 | Zhou Otto Z | Compact microbeam radiation therapy systems and methods for cancer treatment and research |
US8600003B2 (en) | 2009-01-16 | 2013-12-03 | The University Of North Carolina At Chapel Hill | Compact microbeam radiation therapy systems and methods for cancer treatment and research |
US8995608B2 (en) | 2009-01-16 | 2015-03-31 | The University Of North Carolina At Chapel Hill | Compact microbeam radiation therapy systems and methods for cancer treatment and research |
US20120086943A1 (en) * | 2009-03-17 | 2012-04-12 | Tokyo Institute Of Technology | Process for producing nanoparticle monolayers |
US9129969B2 (en) * | 2009-10-01 | 2015-09-08 | Northeastern University | Nanoscale interconnects fabricated by electrical field directed assembly of nanoelements |
US20150137371A1 (en) * | 2009-10-01 | 2015-05-21 | Northeastern University | Nanoscale Interconnects Fabricated by Electrical Field Directed Assembly of Nanoelements |
US9548242B2 (en) | 2009-10-01 | 2017-01-17 | Northeastern University | Nanoscale interconnects fabricated by electrical field directed assembly of nanoelements |
CN101837951A (en) * | 2010-05-24 | 2010-09-22 | 山东大学 | Apparatus and method for graphically producing nano structures by way of electrode induction and microwave curing |
US8358739B2 (en) | 2010-09-03 | 2013-01-22 | The University Of North Carolina At Chapel Hill | Systems and methods for temporal multiplexing X-ray imaging |
CN102169102A (en) * | 2011-01-13 | 2011-08-31 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
US20140050885A1 (en) * | 2011-03-03 | 2014-02-20 | Chrystel Faure | Method for structuring a surface using colloidal particles in an electric field, resultant surfaces and uses thereof |
FR2972201A1 (en) * | 2011-03-03 | 2012-09-07 | Centre Nat Rech Scient | SURFACE STRUCTURING METHOD USING COLLOIDAL PARTICLES UNDER ELECTRIC FIELD, SURFACES OBTAINED AND APPLICATIONS |
WO2012117205A1 (en) * | 2011-03-03 | 2012-09-07 | Centre National De La Recherche Scientifique | Method for structuring a surface using colloidal particles in an electric field, resultant surfaces, and uses thereof |
US9371596B2 (en) * | 2011-03-03 | 2016-06-21 | Centre National De La Recherche | Method for structuring a surface using colloidal particles in an electric field, resultant surfaces and uses thereof |
US20140291296A1 (en) * | 2011-10-12 | 2014-10-02 | The Regents Of The University Of California | Nanomaterials fabricated using spark erosion and other particle fabrication processes |
US9789554B2 (en) * | 2011-10-12 | 2017-10-17 | The Regents Of The University Of California | Nanomaterials fabricated using spark erosion and other particle fabrication processes |
FR2981952A1 (en) * | 2011-11-02 | 2013-05-03 | Fabien Gaben | PROCESS FOR MAKING THIN FILMS DENSED BY ELECTROPHORESIS |
WO2013064776A1 (en) * | 2011-11-02 | 2013-05-10 | Fabien Gaben | Method for producing dense thin films by electrophoresis |
US10577709B2 (en) | 2011-11-02 | 2020-03-03 | I-Ten | Method for producing dense thin films by electrophoresis |
US9634251B2 (en) * | 2012-02-27 | 2017-04-25 | Nantero Inc. | Nanotube solution treated with molecular additive, nanotube film having enhanced adhesion property, and methods for forming the nanotube solution and the nanotube film |
US20130302592A1 (en) * | 2012-05-09 | 2013-11-14 | Korea Institute Of Science And Technology | Method for growth of carbon nanoflakes and carbon nanoflake structure |
US20150364691A1 (en) * | 2014-06-12 | 2015-12-17 | South University Of Science And Technology Of China | Infrared detector with swnt-based double-cantilever and manufacture thereof |
US9782136B2 (en) | 2014-06-17 | 2017-10-10 | The University Of North Carolina At Chapel Hill | Intraoral tomosynthesis systems, methods, and computer readable media for dental imaging |
US9907520B2 (en) | 2014-06-17 | 2018-03-06 | The University Of North Carolina At Chapel Hill | Digital tomosynthesis systems, methods, and computer readable media for intraoral dental tomosynthesis imaging |
US10835199B2 (en) | 2016-02-01 | 2020-11-17 | The University Of North Carolina At Chapel Hill | Optical geometry calibration devices, systems, and related methods for three dimensional x-ray imaging |
US20220028644A1 (en) * | 2018-11-27 | 2022-01-27 | University-Industry Cooperation Group Of Kyung Hee University | Field emission-type tomosynthesis system, emitter for field emission-type tomosynthesis system, and method of manufacturing emitter |
US20210348289A1 (en) * | 2020-05-08 | 2021-11-11 | The Regents Of The University Of California | Guided template based electrokinetic microassembly (tea) |
US11840769B2 (en) * | 2020-05-08 | 2023-12-12 | The Regents Of The University Of California | Guided template based electrokinetic microassembly (TEA) |
WO2023274884A1 (en) | 2021-06-28 | 2023-01-05 | Trevira Gmbh | Electrically conductive yarn |
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EP1474836A4 (en) | 2007-12-05 |
WO2003075372A2 (en) | 2003-09-12 |
AU2002366269A8 (en) | 2003-09-16 |
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CA2468685A1 (en) | 2003-09-12 |
US8002958B2 (en) | 2011-08-23 |
US7887689B2 (en) | 2011-02-15 |
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AU2002366269A1 (en) | 2003-09-16 |
US20050133372A1 (en) | 2005-06-23 |
CN1617954A (en) | 2005-05-18 |
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JP2005519201A (en) | 2005-06-30 |
US20080006534A1 (en) | 2008-01-10 |
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KR20040098623A (en) | 2004-11-20 |
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